BACKGROUND OF THE INVENTION
Field of the Invention
[0001] This invention relates to a light-receiving member for electrophotography having
sensitivity to electromagnetic waves such as light [herein used in a broad sense,
including ultraviolet rays, visible light, infrared rays, X-rays, and y-rays].
Related Background Art
[0002] In the field of image formation, photoconductive materials which form light-receiving
layers in light-receiving members for electrophotography are required to have a high
sensitivity, a high SN ratio [Photocurrent (Ip)/Dark current (Id)], absorption spectral
characteristics matching to those of electromagnetic waves to be irradiated, a rapid
response to light, a desired dark resistance value as well as no harm to human bodies
during usage. Particularly, in the case of a light-receiving member for electrophotography
to be assembled in an electrophotographic device to be used in an office as office
apparatus, the aforesaid harmless characteristic is very important.
[0003] Form the stand point as mentioned above, amorphous silicon [hereinafter represented
as A-Si] has recently attracted attention as a photoconductive material. For example,
German OLS Nos. 2746967 and 2855718 disclose applications of A-Si for use in light-receiving
members for electrophotography.
[0004] Under the-present situation, although the light-receiving members for electrophotography
having light-receiving layers constituted of A-Si of the prior art have been attempted
to be improved respectively and individually with respect to electrical, optical,
photoconductive characteristics such as dark resistance value, photosensitivity, response
to light and environmental characteristics in use and further with respect to stability
with lapse of time and durability, there still remains room to be further improved
in overall characteristics.
[0005] For instance, when improvements to higher photosensitivity and higher dark resistance
were scheduled to be effected at the same time in light-receiving members, residual
potential was frequently observed to remain during use thereof. When such a light-receiving
member was repeatedly used for a long time, various inconveniences were caused such
as accumulation of fatiques by repeated uses or the so-called ghost phenomenon wherein
residual images were formed.
[0006] Also, when constituting the-light-receiving layer of A-Si material, the photoconductive
member may contain as constituent atoms hydrogen atoms or halogen atoms such as fluorine
atoms, chlorine atoms, etc., for improving their electrical, photoconductive characteristics,
boron atoms, phosphorus atoms, etc., for controlling the electroconduction type as
well as other atoms for improving other characteristics. Depending on the manner in
which these constituent atoms are contained, there may sometimes be caused problems
with respect to electrical, photoconductive characteristics or dielectric strength
and further stability of the characteristics with lapse of time of the layer formed.
[0007] That is, the following inconveniences have frequently occurred. For example, the
life of the photocarriers generated by light irradiation in the photoconductive layer
constituting the light-receiving layer is not so long, or the image defect which is
generally called "blank area" and may be considered to be due to the local discharging
breaking phenomenon or the image defect which is generally called "white line" and
may be considered to be formed by friction with a cleaning blade are occurred in the
image transferred onto a transfer paper. Also, when the light-receiving layer has,
for example, a surface layer with a certain film thickness as constituent layer on
the surface thereof and the surface layer is - substantially transparent to the light
used, changes will occur on the reflected spectrum of the surface layer by abrasion
with friction for a long time, whereby undesirable changes occurred with lapse of
time in many cases particularly with respect to sensitivity, etc. Further, when used
in a highly humid atmosphere or used immediately after being left to stand in a highly
humid atmosphere for a long time, the so-called faint image was frequently formed.
[0008] Thus, it is required in designing of a light-receiving member to make elaborations
about layer constitutions, chemical compositions of the respective layers, preparation
methods, etc., so as to solve all of the problems as mentioned above along with the
improvement of A-Si materials per se.
SUMMARY OF THE INVENTION
[0009] An object of the present invention is to solve the various problems in the light-receiving
member for electrophotography having a light-receiving layer of the prior art constituted
of A-Si as described above.
[0010] Another object of the present invention is to provide a light-receiving member for
electrophotography having a light-receiving layer having a photoconductive layer constituted
of A-Si as one of constituent layers having electrical, optical and photoconductive
characteristics which are substantially constantly stable almost without dependence
on the use environment, having excellent light fatigue resistance as well as excellent
durability and humidity resistance without causing any deterioration phenomenon after
repeated uses and being free entirely or substantially from residual potential observed.
[0011] Still another object of the present invention is to provide a light-receiving member
for electrophotography having a light-receiving layer having a photoconductive layer
constituted of A-Si as one of constituent layers having excellent adhesion between
the substrate and the layer provided on the substrate or between the respective layers
laminated, which is dense and stable in structural arrangement and also high in layer
quality.
[0012] Yet another object of the present invention is to provide a light-receiving member
for electrophotography exhibiting excellent electrophotographic characteristics, which
is sufficiently capable of retaining charges at the time of charging treatment for
formation of an electrostatic image to the extent such that conventional electrophotographic
methods can be very effectively applied when it is provided for use as a light-receiving
member for electrophotography.
[0013] Again, another object of the present invention is to provide a light-receiving member
for electrophotography capable of providing easily a high quality image which is high
in density, clear in half tone and -high in resolution, without any image defect or
faint image during prolonged use.
[0014] Yet still another object of the present invention is to provide a light-receiving
member for electrophotography having high photosensitivity, high SN ratio characteristic
and high dielectric strength, and which can be maintained under constant state throughout
the whole period during prolonged use.
[0015] According to the present invention, there is provided a light-receiving member for
electrophotography comprising a substrate and a light-receiving layer on the substrate
comprising photoconductive layer exhibiting photoconductivity comprising an amorphous
material containing at least one of hydrogen atoms and halogen atoms as the constituent
in a matrix of silicon atoms (hereinafter abbreviated as "A-Si(H,X)") and a surface
layer comprising an amorphous material containing silicon atoms, carbon atoms and
hydrogen atoms as the constituents, said surface layer being changed in the distribution
concentration in the layer thickness direction of the carbon atoms such that matching
in optical band gap is obtained at the interface with said photoconductive layer,
and the maximum distribution concentration of the hydrogen atoms within said surface
layer being 41 to 70 atomic percent.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
Figs. lA to lH and 28 to 32 are schematic illustrations of the layer constitutions
of the preferred embodiments of the light-receiving member for electrophotography
of the present invention;
Figs. 2A to 2C and 3 to 5 are schematic illustrations:of unevenness shapes of the
substrate surface and the method for preparing the uneveness shapes;
Figs. 6 to 9 are illustrations showing examples of the distribution states in the
layer thickness direction of carbon atoms and hydrogen atoms in the surface layer;
Figs. 10 to 14 are illustrations showing examples of the distribution states in the
layer thickness direction of the group III atoms and the group V atoms of the periodic
table in the charge injection preventive layer;
Figs. 15 to 21 are illustrations showing examples of the distribution states in the
layer thickness direction of oxygen atoms and/or nitrogen atoms and/or carbon atoms
in the charge injection preventive layer;
Figs. 22-27 are illustrations showing examples of the distribution states in the layer
thickness direction of germanium atoms in the longer wavelength absorbing layer;
Fig. 33 is a schematic illustration of the preparation device according to the glow
discharge method which is an example of the device for forming the light-receiving
layer of the light-receiving member for electrophotography of the present invention;
Fig. 34 and 37-42 are illustrations showing the distribution states of the respective
atoms.
Fig. 35 and 36 are each illustration showing the crosssectional shape of the substrate
used in Examples of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] In the following, the light-receiving member of the present invention is described
in detail referring to the drawings.
[0018] Fig. lA illustrates schematically the layer - constitution of a first preferred embodiment
of the light-receiving member for electrophotography of the present invention.
[0019] The light-receiving member 100 for electrophotography shown in Fig. lA has a light-receiving
layer 102 provided on a substrate 101 for light-receiving member, the light-receiving
layer 102 having a layer constitution comprising a photoconductive layer 103 consisting
of A-Si(H,X) and having photoconductivity and a surface layer 104 constituted of an
amorphous material-containing silicon atoms, carbon atoms, and hydrogen atoms as the
constitutent elements, with the distribution concentrations of the constituent elements
being determined such that matching in optical band gap can be obtained at the interface
with the photocon- ductive layer, and the maximum distribution concen- tration of
hydrogen atoms within the surface layer being 41 to 70 atomic %.
[0020] The light-receiving member for electrophotography of the present invention designed
so as to have the layer constitution as specified above can solve all of the various
problems as mentioned above and exhibits extremely excellent electrical, optical,
photoconductive characteristics, dielectric strength and use environmental characteristic.
[0021] Particularly, there is no influence of the residual potential on image formation
at all, with its electrical characteristic being stable and having high sensitivity
and high SN ratio, as well as excellent light fatigue resistance, repeated use characteristic,
humidity resistance, dielectric strength, whereby the density is high, the half tone
appears clearly, and an image of high resolving power and high quality can be obtained
stably throughout the whole period during use of over a long term.
Substrate
[0022] The substrate to be used in the present invention may be either electroconductive
or insulating. As the electroconductive substrate, there may be mentioned metals such
as NiCr, stainless steel, A1, Cr, Mo, Au, Nb, Ta, V, Ti, Pt, Pd, etc. or alloys thereof.
[0023] As insulating substrates, there may conventionally be used films or sheets of synthetic
resins, including polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene,
polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc., glasses,
ceramics, papers and so on. These insulating substrates should preferably have at
least one surface subjected to electroconductive-treatment, and it is desirable to
provide other layers on the side at which said electroconductive treatment has been
applied.
[0024] For example, electroconductive treatment of a glass can be effected by providing
a thin film of NiCr, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In203, SnO
2, ITO (In
2O
3 + SnO
2) thereon. Alternatively, a synthetic resin film such as polyester film can be subjected
to the electroconductive treatment on its surface by vacuum vapor deposition, electron-beam
deposition or sputtering of a metal such as NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo,
Ir, Nb, Ta, V, Ti, Pt, etc. or by laminating treatment with the metal, thereby imparting
electroconductivity to the surface. The substrate may be shaped in any form such as
cylinders, belts, plates or others, and its form may be determined as desired. For
example, it may desirably be formed into an endless belt or a cylinder for use in
continuous high speed copying. The substrate may have a thickness, which is conveniently
determined so that a light-receiving member as desired may be formed. When the light-receiving
member is required to have a flexibility, the substrate is made as thin as possible,
so far as the function of a support can be exhibited. However, in such a case, the
thickness is generally 10 p or more from the points of fabrication and handling of
the substrate as well as its mechanical strength.
[0025] Particularly, in the case of performing image recording by use of coherent light
such as laser beam, unevenness may be provided on the substrate surface in order to
cancel the image badness by the so-called interference fringe pattern which appears
in the visible image.
[0026] The unevenness to be provided on the substrate surface can be formed by fixing a
bit having a V-shaped cutting blade at a predetermined position on a cutting working
machine such as milling machine, lathe, etc., and cut working accurately the substrate
surface by, for example, moving regularly in a certain direction while rotating a
cylindrical substrate according to a program previously designed as desired, thereby
forming to a desired uneveness shape, pitch and depth. The inverse V-shaped linear
projection produced by the unevenness formed by such a cutting working has a spiral
structure with a center axis of the cylindrical substrate as its center. The spiral
structure of the inverse V-shaped projection may be made into a multiple spiral structure
such as double or triple structure or a crossed spiral structure.
[0027] Alternatively, a parallel line structure along the center axis may also be introduced
in addition to the spiral structure.
[0028] The longitudinal sectional shape of the convexity of the unevenness provided on the
substrate surface is made an inverse V-shape for a managed non- uniformization of
the layer thickness within minute columns of each layer formed and ensuring the good
adhesion and desired electrical contact between the substrate and the layer directly
provided on the substrate, but it should desirably be made substantially isosceles
triangle, right triangle or scalene triangle, as shown in Fig. 2. Among these shapes,
isosceles triangle and right triangle are preferred.
[0029] In the present invention, the respective dimensions of unevenness provided on the
substrate surface under managed state should be set so as to accomplish consequently
the objects of the present invention in view of the points as described below.
[0030] That is, in the first place, the A-Si(H,X) layer constituting the light receiving
layer is sensitive to the state of the surface of the layer formed, and the layer
quality will vary greatly depending on the surface state.
[0031] Therefore, it is necessary to set the dimensions of unevenness provided on the substrate
surface so that lowering in layer quality of the A-Si(H,X) layer may not be brought
about.
[0032] Secondly, if there is an extreme unevenness on the free surface of the light-receiving
layer, it becomes impossible to perform completely cleaning in the cleaning operation
after image formation. Also, when blade cleaning is practiced, there is the problem
that the blade will be damaged sooner.
[0033] As the result of investigations of the problems in layer deposition as described
above, problems in process of electrophotography and the conditions for prevention
of interference fringe pattern, it has been found that the pitch at the concavity
on the substrate surface should preferably be 500 µm to 0.3 µm, more preferably 200
µm to 1 µm, optimally 50 µm to 5 µm.
[0034] It is also desirable that the maximum depth of the concavity should preferably be
made 0.1 µm to 5 µm, more preferably 0.3 um to 3 µm, optimally 0.6 µm to 2 µm. When
the pitch and the maximum depth of the concavity of the substrate surface are within
the ranges as specified above, the gradient of the slanted plane of the concavity
(or the linearly projected portion) - may preferably be 1° to 20°, more preferably
3° to 15°, most preferably 4° to 10°.
[0035] On the other hand, the maximum difference in layer thickness based on the nonuniformness
in layer thickness of the respective layers deposited on such a substrate should preferably
be made 0.1 µm to 2 µm within the same pitch, more preferably 0.1 µm to 1.5 pm, optimally
0.2 µm to 1 µm.
[0036] Also, as an alternative method for cancelling image badness by interference fringe
pattern in the case of using coherent light such as laser beam, unevenness shape with
a plural number of spherical mark recesses may be also provided on the substrate surface.
[0037] That is, the surface of the substrate has more minute unevenness than resolving power
required for the light-receiving member for electrophotography, and yet the unevenness
is formed of a plural number of spherical mark recesses.
[0038] Referring now to Fig. 4 and Fig. 5, the shape of the surface of the substrate in
the light-receiving member for electrophotography and a preferable preparation example
thereof are explained below, but the shape of the substrate in the light-receiving
member of the present invention and its preparation method are not limited by these.
[0039] Fig. 4 illustrates schematically a partially enlarged view of a part of the unevenness
shape according to a typical example of the shape of the surface of the substrate
in the light-receiving member for electrophotography of the present invention.
[0040] In Fig. -4, 1601 represents a substrate, 1602 the surface of substrate, 1603 a rigid
body true sphere and 1604 a spherical mark recess.
[0041] Further, Fig. 4 also shows an example of preferable preparation method for obtaining
the surface shape of the substrate. More specifically, by permitting a rigid body
true sphere 1603 to fall naturally from a position at a predetermined height from
the substrate surface 1602 and be collided against the substrate surface 1602, whereby
a spherical recess 1604 can be formed. And, by use of a plural number of rigid body
true spheres 1603 with substantially the same radius R', and permitting them to fall
simultaneously or successively from the same height h, a plural number of spherical
mark recesses 1604 having the same radius of curvature R and the width D can be formed
on the substrate surface 1602.
[0042] A typical example of the substrate having unevenness shape with a plural number of
spherical mark recesses formed on the surface as described above is shown in Fig.
5. In Fig. 5, 1701 represents a substrate, 1702 the convexity of the unevenness, 1703
a rigid body true sphere and 1704 the concavity of the unevenness.
[0043] In this connection, the radius of curvature R and the width D of the unevenness shape
with the spherical mark recesses on the substrate surface of the light receiving member
for electrophotography of the present invention are important factors for accomplishing
efficiently the effect of preventing generation of interference fringe in the light-receiving
member of the present invention. The present inventors have made various experiments
and consequently found the following facts. That is, when the radius of curvature
R and the width D satisfy the following formula:

0.5 or more Newton ring by shearing interference exists within each mark recess. Further,
when they satisfy the following formula:

one or more Newton ring by shearing interference exists within each mark recess.
[0044] From these facts, in order to disperse the interference fringe generated as a whole
in the light-receiving member, within the respective mark recesses thereby preventing
generation of interference fringe in the light-receiving member, it is desirable that
the above D/R should be made 0.035 or more, preferably 0.055 or more.
[0045] Also, the width D of the unevenness with mark recess should be at most about 500
µm, preferably 200 µm or less, more preferably 100 µm or less.
[0046] Fig. 3 shows an example of the case having a light-receiving layer 1500 comprising
a photoconductive layer 1502 and a surface layer 1503 formed on the substrate 1501
prepared according to the above method. The surface layer 1503 has a free surface
1504.
[0047] In the present invention, in order to achieve its objects effectively, the photoconductive
layer 103, 1502 constituting a part of the light-receiving layer 102, 1500 formed
on the substrate 101, 1501 is constituted of A-Si(H,X) exhibiting photoconductivity
to the irradiated light having the semiconductor characteristics as shown below.
[0048]
(1) p-type A-Si(H,X) ... containing only acceptor; or containing both donor and acceptor
with relatively higher concentration of acceptor (Na);
(2) p-type A-Si(H,X) ... in the type of (1), that containing acceptor with lower acceptor
concentration (Na) than (1), when containing only acceptor, or containing acceptor
with relatively lower concentration as compared with (1), when containing both acceptor
and donor;
(3) n-type A-Si(H,X) ... containing only- donor; or containing both donor and acceptor
with relatively higher concentration of donor (nd);
(4) n-type A-Si(H,X) ... in the type of (3), that containing donor at lower donor concentration
: ; (Nd) than (3), when containing only donor, or containing donor with relatively lower
concentration as compared with (3), when containing both acceptor and donor;
(5) i-type A-Si(H,X) ... Na = Nb ≃ O or Na = Nd
[0049] In the present invention, typical examples of halogen atoms (X) to be incorpprated
in the photoconductive layer 103, 1502 are F, Cℓ, Br and I, especially preferably
F and Cℓ.
[0050] In the present invention, formation of a photoconductive layer 103, 1502 constituted
of A-Si(H,X) may be conducted according to the vacuum deposition method utilizing
discharging phenomenon, such as glow discharge method, microwave discharge method,
sputtering method or ion-plating method. For example, for formation of a photoconductive
layer 103, 1502 constituted of A-Si(H,X) according to the glow discharge method, the
basic process comprises introducing a starting gas for introduction of hydrogen atoms
(
H) and/or a starting gas for introduction of halogen atoms (X) together with a starting
gas for supplying silicon atoms (Si) into the deposition chamber which can be internally
brought to reduced pressure, wherein glow discharge is generated thereby to form a
layer of A-Si (H,X) on the surface of a substrate placed at a predetermined position
in the chamber. When it is to be formed according to the sputtering method, a starting
gas for introduction of hydrogen atoms (H) and/or a gas for introduction of halogen
atoms (X) may be introduced into the chamber for sputtering, when effecting sputtering
upon the target formed of Si in a atmosphere of an inert gas such as Ar, He or a gas
mixture based on these gases.
[0051] The starting gas for supplying Si to be used in the present invention may include
gaseous or gasifiable hydrogenated silicons (silanes) such as
SiH4,
Si2H6,
Si3H
8, Si
4H
10 and others as effective materials. In particular, SiH
4 and Si
2H
6 are preferred with respect to easy handling during layer formation and efficiency
of supplying Si.
[0052] As the effective starting gas for incorporation of halogen atoms to be used in the
present invention, there may be mentioned a number of halogen compounds such as halogen
gases, halides, interhalogen compounds and silane derivatives substituted with halogens
which are gaseous or gasifiable.
[0053] Alternatively, it is also effective in the present invention to use a gaseous or
gasifiable silicon compound containing halogen atoms which is constituted of both
silicon atoms and halogen atoms.
[0054] Typical examples of halogen compounds preferably used in the present invention may
include halogen gases such as of fluorine, chlorine, bromine or.iodine and interhalogen
compounds such as BrF, C1F, ClF
3, BrF
5,
BrF
3, IF
3, IF
7, IC1, IBr, etc.
[0055] z As the silicon compound containing halogen atom, silicon halides such as SiF
4, Si
2F
6, SiCl
4, SiBr
4, or the like are preferred.
[0056] When the specific light-receiving member of this invention is formed according to
the glow discharge method by use of such a silicon compound containing halogen atoms,
it is possible to form a layer constituted of A-Si:H containing halogen atoms (X)
as constituent element on a given substrate without use of a hydrogenated silicon
gas as the starting gas capable of supplying Si.
[0057] In forming the layer containing halogen atoms according to the glow discharge method,
the basic procedure comprises feeding a starting gas for supplying Si, namely a gas
of silicon halide and a gas such as Ar, H
2, He, etc. at a predetermined ratio in a suitable amount into the deposition chamber
for formation of a photoconductive layer, followed by excitation of glow discharge
to form a plasma atmosphere of these gases, thereby forming a photoconductive layer
on a substrate. It is also possible to form a layer by mixing a gas of a silicon compound
containing hydrogen atoms at a suitable ratio with these gases in order to incorporate
hydrogen atoms therein.
[0058] Each of the gases for introduction of respective atoms may be either a single species
or a mixture of plural species at a predetermined ratio.
[0059] For formation of a layer of A-Si(H,X) by the reactive sputtering method or the ion-plating
method, for example, a target of Si is used and sputtering is effected thereon in
a suitable gas plasma atmosphere in the case of the sputtering method. Alternatively,
in the case of ion-plating method, a polycrystalline or single crystalline silicon
is placed as vaporization source in a vapor deposition boat, and the silicon vaporization
source is vaporized by heating by resistance heating method or electron beam method
(EB method) thereby to permit vaporized flying substances to pass through a suitable
gas plasma atmosphere.
[0060] During this procedure, in either of the sputtering method or the ion-plating method,
for introduction of halogen atoms into the layer formed, a gas of a halogen compound
as mentioned above or a silicon compound containing halogen as mentioned above may
be introduced into the deposition chamber to form a plasma atmosphere of the gas therein.
[0061] When hydrogen atoms are to be introduced, a starting gas for introduction of hydrogen
atoms such as H
2 or a
.gas such as silanes as mentioned above may be introduced into the deposition chamber
for sputtering, followed by formation of a plasma atmosphere of the gas.
[0062] In the present invention, as the starting gas for introduction of halogen atoms,
the halogen compounds or silicon compounds pontaining halogens as mentioned above
can effectively be used. In addition, it is also possible to use a gaseous or gasifiable
halide containing hydrogen as one of the constituents such as hydrogen halide, including
FP, HC1, HBr, HI and the like or halo-substituted hydrogenated silicon, including
SiH
2F
2, SiH
2I
2, SiH
2Cl
2, SiHCl
3, SiH
2Br
2, SiHBr
3 and the like as an effective starting material for formation of a photoconductive
layer.
[0063] These halides containing hydrogen atom, which can introduce hydrogen atoms very effectively
for controlling electrical or photoelectric characteristics into the layer during
formation of the photoconductive layer simultaneously with introduction of halogen
atoms, can preferably be used as the starting material for introduction of halogen
atoms.
[0064] For incorporation of hydrogen atoms structurally into the layer, H
2 or a gas of hydrogenated silicon, including SaH
4, Si
2H
6, Si
3H
8, Si
4H
10 and so on may be permitted to be co-present with a silicon compound for supplying
Si in a deposition chamber, wherein dis- charging is excited.
[0065] For example, in the case of the reactive sputtering method, an Si target is used
and a gas for introduction of halogen atoms and H
2 gas are
[0066] introduced together with, if necessary, as inert gas such as He, Ar, etc. into a
deposition chamber, wherein a plasma atmosphere is formed to effect sputtering of
the Si target, thereby forming a layer of A-Si (H,X) on the substrate.
[0067] Further, there may also be introduced a gas such as of B
2H
6 or others in order to effect doping with impurities.
[0068] The amount of hydrogen atoms (H) or halogen atoms (X) incorporated in the photoconductive
layer in the light-receiving member for electrophotography according to the present
invention, or total amount of both of these atoms, may be preferably 1 to 40 atomic
%, more preferably 5 to 30 atomic %.
[0069] The amount of hydrogen atoms (H) and/or halogen atoms (X) in the photoconductive
layer can be controlled by controlling the substrate temperature, the amounts of the
starting materials for incorporation of hydrogen atoms (H) and/or halogen atoms (X)
to be introduced into the deposition device system, the discharging power, etc.
[0070] In the present invention, as the diluting gas to be used during formation of the
photoconductive laxer 103, 1502 according to the glow discharge method or the sputtering
method, there may be employed the so-called rare gases such as He, Ne, Ar, etc., as
preferable ones.
[0071] In.order to make the semiconductor characteristic of the photoconductive layer 103,
1502 a desired one of (1) - (5), n-type impurity, p-type impurity or both impurities
can be incorporated into the layer in a controlled amount during formation of the
layer. As such impurities, p-type impurities may include atoms belonging to the group
III of the periodic table such as B, Al, Ga, In, Tl, etc., as preferable ones, while
n-type impurities may include atoms belonging to the group V of the periodic table
such as N, P, As, Sb, Bi, etc., as preferable ones, particularly preferably B, Ga,
P, Sb, etc.
[0072] In the present invention, when the impurity typified by the atoms belonging to the
group m or V of the periodic table are contained throughout the whole layer region
of the photoconductive layer 103, 1502, the effect of controlling conduction type
and/or conductivity is primarily exhibited.
[0073] The content of the impurity in this case is relatively smaller, preferably 1 x 10-3
to
3 x 102 atomic ppm, more preferably 5 x 10
-3 to 10
2 atomic ppm, optimally 1 x 10-2 to 50 atomic ppm.
[0074] Furthermore, at least one of oxygen atoms and nitrogen atoms may be contained throughout
the whole layer region of the photoconductive layer in amounts which do not impair
the characteristics desired for the photoconductive layer.
[0075] When oxygen atoms are contained in the whole layer region of the photoconductive
layer 103, 1502 in the present invention, primarily the effects of higher dark resistance
and improvement of adhesion between the substrate and the photoconductive layer and
between the photoconductive layer and the surface layer, etc. are brought about. However,
it is desirable that the content of oxygen atoms should be made relatively smaller
in order to avoid deterioration of the photoconductive characteristics of the photoconductive
layer 103, 1502.
[0076] In the case of nitrogen atoms, in addition to the above points, for'example, improvement
of photosensitivity can be effected in the co-presence of the group III atoms, especially
B (boron). The content of oxygen atoms, nitrogen atoms or the sum of both may be preferably
5 x 10
-4 to 30 atomic%, more preferably 1 x 10
-3 to 20 atomic%, optimally 2 x 10
-3 to 15 atomic%.
[0077] For doping of the impurity into the photoconductive layer 103 or 1502, the starting
material for introduction of the impurity may be introduced together with the main
starting materials for formation of the photoconductive layer 103 or 1502 under gaseous
state during layer formation. Such starting material for introduction of the impurity
should be desirably selected which is gaseous under normal temperature and normal
pressure or readily gasifiable at least under the layer forming conditions.
[0078] Specific examples of such starting materials for introduction of the impurities may
include PH3, P
2H
4,
PF3, PF
5, PCl
3, AsH
3,
AsF3 AsF
5,AsCl
3, SbH
3, S
bF3, SbF
5, BiH
3, BF
3, BCl
3,
BBr3, B
2H
6, B
4H
10, B
5H
9, B
5H
11, B
6H
10, B
6H
12, B
6H
14, AlCl
3, GaCl
3, InCl
3, TlCl
3, and the like.
[0079] For incorporating at least one kind of atoms selected from oxygen atoms and nitrogen
atoms, for example, in the case of formation according to the glow discharge method,
a compound containing at least one element of oxygen atoms and nitrogen atoms may
be introduced together with the starting gas for formation of a photoconductive layer
103 or 1502 into a deposition chamber which can be internally brought to reduced pressure,
wherein glow discharge is excited to form a photoconductive layer 103 or 1502.
[0080] Examples of the oxygen atom containing compound as the starting material for introduction
of oxygen atoms may include oxygen (0
2), carbon monoxide (CO), carbon dioxide (CO
2), nitrogen monoxide, nitrogen dioxide, etc.
[0081] As the nitrogen atom containing compounds for the starting material for introduction
of nitrogen atoms, there may be employed, for example, nitrogen (N
2), nitrogen monoxide, nitrogen dioxide, ammonia, etc.
[0082] On the other hand, for example, when the photoconductive layer 103 or 1502 is formed
according to the sputtering method, a target for sputtering molded by mixing the components
comprising, for example, (Si + Si
3N
4) or (Si + SiO
2) at a desired mixing ratio may be used or two sheets of Si wafer and Si
3N
4 wafer or two sheets of Si wafer and SiO
2 wafer may be used as the target for sputtering. Alternatively, a gas of a nitrogen
containing compound or a gas of an oxygen containing compound may be introduced together
with the gas for sputtering such as Ar gas, etc., into a deposition chamber, where
sputtering may be effected with the use of Si as the target to form a photoconductive
layer 103 or 1502.
[0083] During formation of the photoconductive layer 103 or 1502, the substrate temperature
during layer formation is an important factor which influences the structure and the
characteristic of the layer to be formed, and in the present invention, the substrate
temperature during layer formation should desirably be controlled strictly so that
the photoconductive layer 103 or 1502 having the intended characteristic may be prepared
as desired.
[0084] The substrate temperature during formation of the photoconductive layer 103 or 1502
for the purpose of accomplishing effectively the objects of the present invention,
should be selected within the optimum range corresponding to the method for formation
of the photoconductive layer 103 or 1502 to practice formation of the photoconductive
layer 103 or 1502, but it may be generally 50°C to 350°C, preferably 100°C to 300°C.
For formation of the photoconductive layer 103 or 1502, it is advantageous to employ
the glow discharge method or the sputtering method for the reasons such as relatively
easier severe control of the composition ratio of the atoms constituting the layer
or control of the layer thickness, and in the case of forming a photoconductive layer
103 or 1502 according to these layer forming methods, discharging power or gas pressure
during layer formation is also one of important factors influencing the characteristic
of the photoconductive layer 103 or 1502 to be prepared similarly as the above substrate
temperature.
[0085] The discharging power condition for preparing effectively the photoconductive layer
103 or 1502 having the characteristics for accomplishing the objects in the present
invention with good productivity may be generally 10 to 1000 W, preferably 20 to 500
W. The gas pressure within the deposition chamber may be generally 0.01 to 1 Torr,
preferably about 0.1 to 0.5 Torr.
-
[0086] In the present invention, the numerical value ranges desirable for the substrate
temperature, discharging power during formation of the photoconductive layer 103 or
1502 may be the values within the ranges as mentioned above, but these layer forming
factors,are not determined independently and separately, but it is desirable that
the optimum values for the factors for forming respective layers should be determined
based on the mutual organic relationship so that a photoconductive layer 103 or 1502
with desired characteristics may be formed.
[0087] The layer thickness of the photoconductive layer 103 or 1502 may be determined suitably
as desired so that the photocarriers generated by irradiation of a light having desired
spectral characteristic may be transported with good efficiency, and it is preferably
1 to 100 u, more preferably 2 to 50 µ.
[0088] The surface layer 104 or 1503 formed on the photoconductive layer 103 or 1502 has
a free surface 105 or 15.04, which is provided primarily for accomplishing the objects
of the present invention in humidity resistance, continuous repeated use characteristic,
dielectric strength, use environment characteristic, durability, etc.
[0089] And, in the light-receiving member of the present invention, it is an extremely important
point that the optical band gaps Eg opt of the both layers at the interface between
the surface layer 104 or 1503 and the photoconductive layer 103 or 1502 should be
matched to each other or matched at least to the extent which can prevent substantially
reflection of the incident light at the interface between the surface layer 104 or
1503 and the photoconductive layer 103 or 1502, and it is also an important point
that this presents an extremely specific preferable condition in relationship with
the hydrogen content. Further, in the present invention, it is necessary to set the
hydrogen content at the region near the surface of the surface layer 104 or 1503,
at least at the outermost surface at a predetermined concentration.
[0090] For satisfying the various conditions as mentioned above, the distribution states
of the constituent elements within the surface layer 104 or 1503 are required to be
determined under strict condition control.
[0091] Further, in addition to the conditions as described above, at the end portion on
the free surface side of the surface layer 104 or 1503, it is also another point of
consideration to constitute the optical band gap Eg opt possessed by the surface layer
104 or 1503 sufficiently great at the end portion on the free surface side of the
surface-layer 104 or 1503 in order to ensure-sufficiently the dose of incident light
reaching the photoconductive layer 103 or 1502 provided beneath the surface layer
104 or 1503. And, simultaneously with constitution so that optical band gaps Eg opt
may be matched at the interface between the surface layer 104 or 1503 and the photoconductive
layer 103 or 1502, when the optical band gap Eg opt is constituted sufficiently great
at the end portion of the free surface side of the surface layer 104-or 1503, the
optical band gap Eg opt possessed by the surface layer 104 or 1503 is constituted
so as to contain at least the region wherein it is continuously changed in the layer
thickness direction of the surface layer 104 or 1503.
[0092] For controlling the values of optical band gap Eg opt in the surface layer 104 or
1503 in the layer thickness direction, it can be typically practiced by controlling
of the amount of the carbon atom (C) which is the main controlling atom for the optical
band gap Eg opt to be contained in the surface layer 104 or 1503, and also for the
hydrogen atoms having the function of matching other characteristics of the surface
layer 104 or 1503 to the optimum condition in the form corresponding to the change
in optical band gap Eg opt, its content is controlled to a specific distribution state.
[0093] Referring now to Fig. 6 through Fig. 9, some typical examples of distribution states
of carbon atoms and hydrogen atoms in the layer thickness direction of the surface
layer 104 or 1503 are described, but the present invention is not limited by these
examples.
[0094] In Figs. 6 through 9, the axis of abscissa indicates the distributed concentration
C of the carbon atoms (C), silicon atoms (Si), and hydrogen atoms (H), and the axis
of ordinate the layer thickness t of the surface layer. In the Figures, t
T shows the interface position between the photoconductive layer and the surface layer,
t
F the free surface position, the solid line the change in distributed concentration
of the carbon atoms (C), the two-dot chain line the change in the distributed concentration
of silicon atoms (Si), and the one-dot chain line the change in distributed concentration
of hydrogen atoms (H), respectively.
[0095] Fig. 6 shows a first typical example of the distributed state in the layer thickness
of the atoms (C), silicon atoms (Si), and hydrogen atoms (H) to be contained in the
surface layer. In said example, from the interface position t
T to the position t
1, the distributed concentration C of the atoms (C) is increased from 0 to the concentration
C
l as a first order function, while the distributed concentration of silicon atoms is
reduced from the concentration C
2 to the concentration C
3 as a first order function and the distributed concentration of hydrogen atoms in
increased from C
4 to C
5 as a first order function. From the position t
l to the position t
F, the distributed concentration C of the atoms (C) and silicon atoins and hydrogen
atoms maintain the constant values of the respective concentrations C
1, C
3, and C
5, respectively. Here, for convenience in explanation, the inflection points of the
distributed states of the respective components are all made t
l, but there is substantially no trouble if they may be deviated from one another.
[0096] In the example shown in Fig. 7, from the position t
T to the position t
F, the carbon atoms (C) are varied from 0 to the concentration C
6, the silicon atoms (Si) from C
7 to C
8, and the hydrogen atoms (H) from C
9 to C
10, respectively, as a first order function. In the case of this example, since the
components are varied over the entire region of the surface layer, the troubles caused
by discontinuity of the components can be further improved.
[0097] Also, it is possible to use, for example, the patterns in which the change rates
of the components are varied from time to time as shown in Figs. 8 and 9 and a combination
of the typical examples as described with reference to Figs. 6 to 9, which can be
selected suitably depending on the desired film characteristics or the conditions
in the preparation. apparatus, etc. Further, matching in optical band gap Eg opt of
the interface may be a substantially sufficient value, and in that sense the carbon
content at t
T is not limited to 0, but may also have a finite value, and also stagnation in change
of the components in the distributed region for a certain interval may be also permissible
from this standpoint.
[0098] Formation of the surface layer 104 or 1503 may be practiced according to the glow
discharge method, the microwave discharge method, the sputtering method, the ion implantation
method, the ion plating method, the electron beam method, etc. These preparation methods
may be employed by suitable selection depending on the factors such as preparation
conditions, the degree of load of installation investment, preparation scale, the
desired characteristics for the light-receiving number for electrophotography to be
prepared, but the glow discharge method or the sputtering method may be preferably
employed for such advantages as relatively easy control of the preparation conditions
for preparing the light-receiving member for electrophotography having desired characteristics,
easy introduction of carbon atoms and hydrogen atoms together with silicon atoms into
the surface layer 104 or 1503, etc.
[0099] Further, in the present invention, the surface layer 104 or 1503 may be formed by
using the glow discharge method and the sputtering method in combination in the same
apparatus system.
[0100] For formation of the surface layer 104-or 1503 by the glow discharge method, the
basic procedure may be the same in the distributed region or the constant region of
the constituents, and comprises introducing the starting gases for formation of A
-(
Si xC
1-x )
y: H
1-y optionally mixed with a diluting gas at a desired mixing ratio, into a deposition
chamber for vacuum deposition in which a substrate 101 or 1501 is placed, and exciting
glow discharging of the gases introduced to form a gas plasma, thereby depositing
A(Si
xC
1-x)
y: H
1-y on the photoconductive layer 103 or 1502 already formed on the above substrate 101
or 1501. Formation of the distributed region can be easily done by setting the components
to be changed, for example, flow rates of a carbon atom containing gas, of a silicon
atom containing gas, and of a hydrogen atom containing gas, etc., respectively, to
a desired distribution pattern from the flow rate on start-up and increasing the flow
rates following a specific sequence.
[0101] In the present invention, as the starting gases for formation of A-(Si C
1-x)
y:H
1-y most of the gaseous substances or gasified gasifiable substances containing at least
one of Si, C, and H as the constituent atoms can be used.
[0102] When employing a starting material gas containing Si as one of Si, C, and H as the
constituent atom, for example, a starting gas containing Si as the constituent atom,
a starting material gas containing C as the constituent atom, and a starting gas containing
H as the constituent atom may be used by mixing at a desired mixing ratio, or alternatively
a starting material gas containing Si as the constituent atom, and a starting gas
containing C and H as the constituent atoms may be mixed also at a desired ratio,
or a starting gas containing Si as the constituent atom may be used as a mixture with
a starting material gas containing the three constituent atoms of Si, C, and H.
[0103] Also, it is possible to use a mixture of a starting material gas containing Si and
H as the constituent atoms with a starting material gas containing C as the constituent
atom. Also, in the distributed region, the above mixing ratio may be varied following
a predetermined sequence.
[0104] The substance effectively used as the starting materials for formation of the surface
layer 104 or 1503 in the present invention may include hydrogenated silicon hydride
gases constituted of silicon atoms (Si) and hydrogen atoms (H) such as silane, as
exemplified by
SiH4, Si2H6, Si
3H
8, Si
4H
10, etc., hydrocarbons constituted of C and H such as saturated hydrocarbons having
1 to 4 carbon atoms, ethylenic hydrocarbons having 2 to 4 carbon atoms or acetylenic
hydrocarbons having 2 to 3 carbon atoms.
[0105] More specifically, typical examples are saturated hydrocarbons such as methane (CH
4), ethane (C
2H
6), propane (C
3H
8), n-butane (n-C
4H
10), pentane (C
5H
12), and the like; ethylenic hydrocarbons such as ethylene (C
2H
4), propylene (C
3H
6), butene-1 (C
4H
8), butene-2 (C
4H
8), isobutylene (C
4H
8),
pe
ntene (C
5H
10), and the like; and acetylenic hydrocarbons such as acetylene (
C2H2), methylacetylene (C
3H
4), butyne (C
4H
6), and the like.
[0106] Typical examples of the starting gas having Si, C, and H as constituent atoms are
alkyl silanes such as Si(CH
3)
4, Si(C
2H
5)
4, and the like. In addition to these starting gases, H
2 can of course be effectively used as the starting gas for introduction of hydrogen
atoms (H).
[0107] For formation of the surface layer 104 or 1503 by the sputtering method, a single
crystalline or polycrystalline Si wafer or C wafer or a wafer containing Si and C
mixed therein is used as a target and subjected to sputtering in an atmosphere of
various gases.
[0108] For example, when Si wafer is used as target, a starting gas for introduction of
C and H, which may be diluted with a diluting gas, if desired, is introduced into
a deposition chamber for sputter to form a gas plasma of these gases therein and effect
sputtering of said Si wafer. The distributed region in this case may be formed by,
for example, varying the concentration of the starting material gas containing C following
a certain sequence.
[0109] Alternatively, Si and C as separate targets or one sheet target of a mixture of Si
and C can be used and sputtering is
:effected in a gas atmosphere containing at least hydrogen atoms. The distributed region
in this case isrequired to be formed by using a gas containing either one of C or
Si in combination and varying these gas concentrations following a certain sequence.
[0110] As the starting gas for introduction of C or H, there may be employed those as mentioned
in the glow discharge method as described above as effective gases also in the case
of sputtering.
[0111] In the present invention, as the diluting gas to be employed in forming the surface
layer 104 or 1503 according to the glow discharge method or the sputtering method,
there may be included so called rare gases such as He, Ne or Ar as suitable ones.
[0112] The surface layer 104 or 1503 in the present invention is formed carefully so that
it may have a distributed region along the spirit of the present invention as described
above and the characteristics required from the view point of entire layers may be
given exactly as desired.
[0113] That is, a substance constituted of Si, C and -H, can take various forms from crystalline
to amorphous, electrical properties from conductive through semiconductive to insulating,
and photoconductive properties from photoconductive to nonphotoconductive depending
on the preparation conductions. In the present invention, the preparation conditions
are severely selected as desired so that there may be formed A-Si
xC
1-x having desired characteristics depending on the purposes.
[0114] For example, for providing the surface layer 104 or 1503 primarily for the purpose
of improving dielectric strength, A-(Si C
1-x)
y:H
1-y is arranged as x
1-y an amorphous material with remarkable electrical insulating behaviors in the use
environment.
[0115] On the other hand, when the surface layer 104 or 1503 is provided primarily for the
purpose of improving continuous repeated use characteristics or use environmental
characteristics, the degree of the above electrical insulating property is alleviated
to some extent and A-(Si C
1-x)
y :H
1-y is arranged as an amorphous material having some sensitivity to the light irradiated.
[0116] During formation of the surface layer 104 or 1503 comprising A-(Si C
1-x)
y :H
1-y on the surface of x the photoconductive layer 103 or 1502, the substrate temperature
during layer formation is an important factor which influences the structure and the
characteristic of the layer to be formed and, in the present invention, the substrate
temperature during layer formation should desirably be controlled strictly so that
A-(Si
xC
1-x)
y :H
1-y having desired characteristics may be prepared as desired.
[0117] As the substrate temperature during formation of the surface layer 104 or 1503 accomplishing
effectively the object in the present invention, a suitable optimal range corresponding
to the formation method of the surface layer 104 or 1503 may be selected to practice
formation of the surface layer 104 or 1503, but is may be preferably 50°C to 350°C,
more preferably 100°C to 300°C. For formation of the surface layer 104 or 1503, it
is advantageous to employ the glow discharge method or the sputtering method for such
reasons as relatively easier severe control of the composition ratio of the atoms
constituting the layer or the control of layer thickness as compared with other methods.
For formation of the surface layer 104 or 1503 according to these layer forming methods,
the discharging power or the gas pressure during layer formation is one of important
factors influencing the characteristics of A-(Si
xC
1-x)
y:H
1-y prepared.
[0118] The discharging power condition for preparing effectively A-(Si
xC
1-x)
y:H
1-y having the characteristics for accomplishing the objects in the present invention
with good productivity may be preferably 10 to 1000 W, more preferably 20 to 500 W.
The gas pressure in the deposition in chamber may be preferably 0.01 to 1 Torr, more
preferably 0.1 to 0.5 Torr.
[0119] In the present invention, the desirable numerical value ranges for the substrate
temperature and discharging power during formation of the surface layer 104 or 1503
may be those as mentioned above, but these layer formation factors are not determined
independently and separately, but it is desirable that the optimum values of the respective
layer formation factors are desirably determined based on the mutual organic relationship
so that the surface layer 104 or 1503 comprising A-(Si
xC
1-x)
y:H
1-y having desired characteristics may be formed.
[0120] The amounts of carbon atoms and hydrogen atoms contained in the surface layer 104
or 1503 in the light-receiving member for electrophotography of the present invention
are also important factors for forming the surface layer 104 or 1503 having the desired
characteristics to accomplish the objects of the present invention similarly as the
preparation conditions of the surface layer 104 or 1503.
[0121] The amount of the carbon atoms contained in the surface layer 104 or 1503 in the
present invention should be desirably varied in the distributed region preferably
from 1 x 10 to 90 atomic %, more preferably 1 x 10
-4 to 85 atomic %, optimally from 1 x 10
-4 to 80 atomic % based on the total amounts of silicon atoms and carbon atoms,, and
also should desirably in the constant region preferably 1 x 10
-3 to:90 atomic %, more preferably 1 to 90 atomic %, optimally 10 to 80 atomic %. The
content of hydrogen atoms should be desirably made constant or varied in the distributed
region within the range from 1 to 70 atomic % based on the total amount of the constituent
atoms, and also should be desirably made in the constant region or at least on the
outermost surface of the surface layer preferably 41 to 70 atomic %, more preferably
45 to 60 atomic %.
[0122] The light-receiving member having the surface layer prepared under the quantitative
range as specified above and the above distributed state and further the above preparation
conditions can be applied sufficiently as the material which is extremely excellent
as not found in the prior art in practical aspect.
[0123] Referring to several examples, its action is described.
[0124] To describe about the aspect of matching in band gap, for example, when there exists
a clear optical interface between the surface layer and the photoconductive layer
as in the case of the prior art, reflection of incident light occurs at said interface,
whereby there is observed the phenomenon that the dose of the incident light into
the photoconductive layer may be more or less influenced by the interference between
this reflection at said interface and the reflection at the free surface. Particularly,
when coherent light such as laser beam is used as the light source, this tendency
is marked. On the other hand, in the case of a copying machine using, for example,
the blade cleaning method, the surface layer will be inevitably more or less abraded
by prolonged use, and the film thickness change of the surface layer by this abrasion
will cause a change in the above interference state. That is, there is observed the
phenomenon that the dose of incident light into the photoconductive layer will be
more or less influenced by the abrasion. Controlling of matching in band gap in the
present invention has one aspect of bringing about the effect of minimizing reflection
at the above interface from the aspect of continuity of the components, and also separately
imparts continuity to light absorption itself by changing the band gap, thus giving
rise to double preferable actions. Accordingly, the action which should be specially
mentioned in this case may be said to be the outstanding effect concerning particularly
maintenance of the characteristics during prolonged use among the preferable electrophotographic
various characteristics as already described.
[0125] r Next, the role of hydrogen in the surface layer is described. The defects existing
within the surface layer (primarily dangling bonds of silicon atoms or carbon atoms)
have been known to exert bad influences on the characteristics as the light-receiving
member for electrophotography. For example, there may be caused deteriorat-on of charging
characteristics by injection of charges from the free surface, fluctuation in charging
characteristics due to change in the surface structure under the use environment such
as high humidity, and further residual image phenomenon during repeated use by injection
of charges from the photoconductive layer to the surface layer during corona charging
or light irradiation and trapping of the charges by the defects within the surface
layer as mentioned above.
[0126] However, by controlling the hydrogen content within the surface layer in at least
the outermost surface region to 41 atomic % or higher, all of the above problems can
be cancelled, and particularly a dramatic improvement can be effected in the electrical
characteristics and high speed continuous use characteristic as compared with the
prior art product.
[0127] On the other hand, if the hydrogen content in the above surface becomes 71 atomic
% or higher, the hardness of the surface layer will be lowered, whereby the light-receiving
member cannot stand repeated uses. Therefore, it is one of very important factors
in obtaining extremely excellent desired electrophotographic characteristics to control
the hydrogen content in the surface layer within the range as specified above. The
hydrogen content in the: surface layer can be controlled by the flow rate of H
2 gas, the substrate temperature, the discharging power, the gas pressure, etc.
t
[0128] There is also a specific relationship between the above matching in the optical band
gap Eg opt and the hydrogen atoms containing state. Particularly, in the distributed
region of carbon atoms (C) which is the representative change component of the optical
band gap Eg opt, the hydrogen containing state is such that its content is set so
as to optimize the structure in that region or/and minimize dangling bonds, and also
so as to become the value necessary for effecting the action as described in the role
of hydrogen in the above surface layer. In other words, it is set in the most natural
form to make the content of hydrogen atoms increased toward at least the free surface
side.
[0129] Thus, the hydrogen atoms containing state in the surface layer in the present invention
can be also said to have another action of taking matching between the following both
actions so that the action of matching in the optical band gap Eg opt and the action
by the hydrogen atoms content itself may be both exhibited to full extent.
[0130] The numerical range of the layer thickness in the present invention is one of the
important factors for accomplishing effectively the objects of the present invention.
[0131] The numerical range of the layer thickness of the surface layer 104 or 1503 in the
present invention may be determined suitably as desired depending on the initial purpose
so that the objects of the present invention can be effectively accomplished.
[0132] Also, the layer thickness of the surface layer 104 or 1503 is required to be determined
suitably in relationship with the layer thickness of the photoconductive layer 103
or 1502, as desired under the organic relationship corresponding to the characteristics
demanded for the respective layer regions. Further, in addition, it is desirably determined
in view of economical considerations including productivity or bulk productivity.
[0133] The layer thickness of the surface layer 104 or 1503 in the present invention should
be desirably be made generally 0.003 to 30 µ, preferably 0.004 to 20 µ, optimally
0.005 to 10 p.
[0134] The layer thickness of the light-receiving layer of the light-receiving member 100
for electrophotography in the present invention may be determined suitably as desired
as fitted for the purpose.
[0135] In the present invention, the layer thickness of the light-receiving layer 102 or
1500 may be determined suitably as desired in the layer thickness relationship between
the photoconductive layer 103 or 1502 and the surface layer 104 or 1503 so that the
characteristics imparted to the photoconductive layer 103 or 1502 and the surface
layer 104 or 1503 constituting the light-receiving layer 102 or 1500 can be effectively
utilized respectively to accomplish effectively the objects of the present invention,
and it is preferable that the layer thickness of the photoconductive layer 103 or
1502 should be made some hundred to some thousand-fold or more relative to the layer
thickness of the surface layer 104 or 1503.
[0136] In the light-receiving member for electrophotography of the present invention, for
further improvement of adhesion between the substrate 101 or 1501 and the photoconductive
layer 103 or 1502, there may be also provided an adhesion layer constituted of, for
example, amorphous materials containing at least one of Si
3N
4, SiO
2, SiO, hydrogen atoms, and halogen atoms and at least one of nitrogen atoms, oxygen
atoms, and carbon atoms and silicon atoms, etc.
[0137] Fig. lB shows an example of the light-receiving member for electrophotography having
such a layer constitution.
[0138] The light-receiving member for electrophotography 200 shown in Fig. lB has the same
layer constitution as the light-receiving layer for electrophotography 100 shown in
Fig. 1A except for having an adhesion layer 206. That is, on the adhesion layer 206
are provided successively the photoconductive layer 203 and the surface layer 204,
and the photoconductive layer 203 is constituted of the same material and has the
sameifunction as the photoconductive layer 103, and also the surface layer 204 as
the surface layer 104.
Adhesion layer
[0139] The adhesion layer of the light-receiving member for electrophotography in the present
invention is constituted of an amorphous or polycrystalline material containing at
least one of nitrogen atoms, oxygen atoms and carbon atoms, silicon atoms and optionally
at least one of hydrogen atoms and halogen atoms. Further, the above adhesion layer
206 may also contain a substance for controlling conductivity (valence electron controller)
as the constituent atom.
[0140] That is, the primary object of said adhesion layer is to improve adhesion between
the substrate and the photoconductive layer. Also, by containing a substance for controlling
conductivity in said layer, the transport of charges between the substrate and the
photoconductive layer can be effected more efficiently.
[0141] Nitrogen atoms, oxygen atoms, carbon atoms, hydrogen atoms, halogen atoms and the
substance for controlling conductivity may be contained either uniformly throughout
said layer or under nonuniform distribution state in-the layer thickness direction.
[0142] The amount of carbon atoms, oxygen atoms or nitrogen atoms contained in the adhesion
layer formed in the present invention or the combined amount of at least two of them
must be determined suitably as desired, but it may preferably be 0.0005 to 70 atomic
%, more preferably 0.001 to 50 atomic %, optimally 0.002 to 30 atomic %.
[0143] The layer thickness of the adhesion layer 206 may be determined suitably in view
of adhesion property, transport efficiency of charge, production efficienty, but it
may preferably be 0.01 to 10 µm, more preferably 0.02 to 5 µm.
[0144] The amount of hydrogen atoms, the amount of halogen atoms or the sum of the amounts
of hydrogen atoms and halogen atoms contained in the adhesion layer may preferably
be 0.1 to 70 atomic %, more preferably 0.5 to 50 atomic %, optimally 1.0 to 30 atomic
%.
[0145] Fig. lC and Fig. 1D illustrate schematically layer constitutions of the third preferred
embodiment and the fourth preferred embodiment, respectively, of the light-receiving
member for electrophotography of the present invention.
[0146] The light-receiving member for electrophotography shown in Fig. 1C and Fig. 1D has
a light-receiving layer 300, 400 on a substrate 301, 401 for light-receiving member,
said light-receiving layer 300, 400 having a layer constitution, comprising a charge
injection preventive layer 302, 402, a photoconductive layer 303, 403 having photoconductivity
and a surface layer 304, 404. Also, 406 represents an adhesion layer.
[0147] The photoconductive layers 303, 403, the surface layers 304, 404, the adhesion layer
404 in Figs. 1C and 1D are respectively the same as the photoconductive layers 103,
203, the surface layers 104, 204 and the adhesion layer 206 shown in Figs. lA and
lB, and therefore description of these layers is omitted.
[0148] The charge injection preventive layers 302, 402 newly added in the light-receiving
member for electrophotography shown in Figs. 1C and lD are described in detail below.
Charge Injection Preventive Layer
[0149] The charge injection preventive layer 302, 402 in the present invention is constituted
of A-Si (H,
X) or polycrystalline silicon and contains a substance for controlling conductivity
(valence electron controller) uniformly throughout the whole layer region or preferably
nonuniformly as enriched on the substrate side in said layer 302, 402. Further, if
necessary, oxygen atomsor/and nitrogen atoms or/and carbon atoms may be contained
uniformly throughout the whole layer region or a partial layer region of said layer
102 or preferably nonuniformly as enriched on the substrate side, whereby improvement
of adhesion between the charge injection preventive layer 102 and the substrate and
control of band gap can be effected.
[0150] As the substance for controlling conductivity - to be contained in the charge injection
preventive layer 302, 402, there may be mentioned so called impurities in the field
of semiconductors similarly as in above description of photoconductive layer. In the
present invention, there may be employed the atoms belonging to the group III of the
periodic table giving p-type conductivity characteristics (the group III atoms) or
the atoms belonging to the group V atoms of the periodic table giving n-type conductivity
characteristics (the group V atoms).
[0151] Figs. 10 through 14 show typical examples of distributed states in the layer thickness
direction of the group III atoms or the group V atoms contained in the charge injection
preventive layer 302, 402. In Figs. 10 through 14, the axis of abscissa indictes the
distributed concentration C of the group III atoms or the group V atoms, and the axis
of ordinate the layer thickness t of the charge injection preventive layer 302, 402
t
B showing the interface position on the substrate 301, 401 side, t
T the interface position on the side opposite to the substrate 301, 401 side. That
is, the charge injection preventive layer is formed from the t
B side toward the t
T side.
[0152] Fig. 10 shows a first typical example of the distributed state in the layer thickness
direction of the group III atoms or the group V atoms contained in the charge injection
preventive layer 302, 402.
[0153] In the example shown in Fig. 10, from the interface position t
B to the position t
1, the group III atoms or the group V atoms are contained with the concentration C
taking a constant value of C
1, and the distributed concentration C being reduced from C
22 gradually and continuously from the position t
1 to the interface position t
T. At the interface position t
T, the distributed concentration is made C
23.
-
[0154] In the example shown in Fig. 11, the distributed concentration C of the group III
atoms or the group V atoms contained is reduced from C
24 gradually and continuously from the position t
B to the position t
T, until it becomes C
25 at the position t
T.
[0155] In the example shown in Fig. 12, the distributed concentration C of the group III
atoms or the group V atoms is a constant value of C
26 between the position t
B and the position t
2 and made C27 at the position t
T. Between the position t
2 and the position t
T, the distributed concentration C is reduced as a first order function from the position
t
2 to the position
tT.
[0156] In the example shown in Fig. 13, the distributed concentration C takes a constant
value of C
28 from the position t
B to the position t
3, and is reduced from C
29 to C
30 as a first order function from the position t
3 to the position t
T.
[0157] In the example shown in Fig. 14, the distributed concentration C takes a constant
value of C31 from the position t
B to the position t
T.
[0158] In the present invention, when the charge injection preventive layer 302, 402 contains
the group III atoms or the group V atoms in the distribution state where they are
enriched on the substrate side, it is preferable that the layer should be formed to
a distribution state such that the maximum value of the distributed concentration
value of the group III atoms or the group V atoms may be 50 atomic ppm or more, more
preferably 80 atomic ppm or more, optimally 100 atomic ppm or more.
[0159] In the present invention, the content of the group III atoms or the group V atoms
in the charge injection preventive layer 302, 402 may be determined suitably as desired
so as to accomplish effectively the objects of the present invention, but preferably
30 to 5 x 10
4 atomic ppm, more preferably 50 to 1 x 10
4 atomic ppm, optimally 1 x 10
2 to 5 x 10
3 atomic ppm.
[0160] The charge injection preventive layer 302, 402 has the effect of primarily improving
adhesion between the substrate 301, 401 and the charge injection preventive layer
302, 402, improving adhesion between the charge injection preventive layer 302, 402
and the photoconductive layer 303, 403 or controlling the band gap Egopt of the charge
injection preventive layer 302, 402 by containment of oxygen atoms or/and nitrogen
atoms or/and carbon atoms as mentioned above.
[0161] Figs. 15 through 21 show typical examples of distribution states in the layer thickness
direction of oxygen atoms or/and nitrogen atoms or/and carbon atoms to be contained
in the charge injection preventive layer 302, 402. In the examples shown in Figs.
15 through 21, the axis of abscissa indicates the distributed concentration C of oxygen
atoms or/and nitrogen atoms or/and carbon atoms, and the axis of ordinate the layer
thickness t of the charge injection preventive layer 302, 402, t
B showing the interface position on the substrate side and the t
T the interface position on the side opposite to the substrate side. That is, the charge
injection preventive layer is formed from the t
B side toward the t
T side.
[0162] In Fig. 15, there is shown a first typical example in which the distribution state
in the layer thickness direction of oxygen atoms or/and nitrogen atoms or/and carbon
atoms contained in the charge injection preventive layer 302, 402.
[0163] In the example shown in Fig. 15, from the interface position t
B to the position t
4, oxygen atoms or/and nitrogen atoms or/and carbon atoms are contained while the concentration
C taking a constant value of C
32, and the distributed concentration C is gradually and continuously reduced from C
33 from the position t
4 to the interface position t
T. At the interface position t
T, the distributed concentration is made C
34.
[0164] In the example shown in Fig. 16, the distributed concentration C of oxygen atoms
or/and nitrogen atoms or/and carbon atoms contained is reduced gradually and continuously
from C
35 from the position t
B to the position t
T, and at the position t
T the concentration becomes C
36.
[0165] In the case of Fig. 17, the distributed concentration C of oxygen atoms or/and nitrogen
atoms or/and carbon atoms is made a constant value C
37 from the position t
B to the position t
5, and reduced gradually and continuously from C
38 between the position t
5 and the position t
T, until it is made substantially zero at the position t
T.
[0166] In the case of Fig. 18, the distributed concentration C of oxygen atoms or/and nitrogen
atoms or/and carbon atoms is reduced gradually and continuously from C
39 from the position t
B to the position t
T, until it is made substantially zero at the position
tT.
[0167] In the example shown in Fig. 19, the distributed concentration C of oxygen atoms
or/and nitrogen atoms or/and carbon atoms takes a constant value of C
40 from the position t
B to the position t
6, and reduced as a first order function from C
40 to C
41 from the position t
6 to the position t
T.
[0168] In the example shown in Fig. 20, the distributed concentration C of oxygen atoms
or/and nitrogen atoms or/and carbon atoms is a constant value of C
42 between the position t
B and the position t
7, and made C
44 at the position t
T. Between the position t
6 and the position t
T, the distributed concentration C is reduced as a first order concentration from C43
at the position t
6 to C
44 at the position t
T.
[0169] In the example shown in Fig. 21, the distributed concentration takes a constant value
of C
45 45 from the position t
B to the position t .
[0170] In the present invention, when the charge injection preventive layer 302, 402 contains
oxygen atoms or/and nitrogen atoms or/and carbon atoms in a distribution state as
enriched on the substrate 301, 401 side, it is preferable that the maximum value of
the distribution concentration value of oxygen atoms or/and nitrogen atoms or/and
carbon atoms or the sum of those of two kinds amongthem should be 500 atomic ppm or
more, preferably 800 ppm or more, optimally 1000 atomic ppm or more.
[0171] In the present invention, the content of oxygen atoms or/and nitrogen atoms or/and
carbon atoms or the sum of those of two kinds among them contained in the charge injection
preventive layer 302, 402 may be determined suitably as desired so as the accomplish
effectively the objects of the present invention, but may be preferably 0.001 to 50
atomic more preferably 0.002 to 40 atomic %, optimally 0.003 to 30 atomic %.
[0172] In the present invention, the layer thickness- of the charge injection preventive
layer may be preferably 0.01 to 10 µ, more preferably 0.05 to 8 µ, optimally 0.1 to
5 µ, for obtaining desired electrophotographic characteristics and also from the standpoint
of economy.
[0173] In the present invention, halogen atoms (X) : contained in the charge injection preventive
layer 302, 402 may preferably be F, Cl, Br, I, particularly F, Cl.
[0174] In the present invention, for formation of a charge injection preventive layer constituted
of a polycrystalline silicon or A-Si(H,X), for example, there may be employed the
vacuum deposition method utilizing discharging phenomenon such as the glow discharge
method, the microwave discharge method, the sputtering method or the ion plating method.
For example, for formation of a layer constituted of a polycrystalline silicon or
A-Si(H,X), the basic procedure comprises introducing a starting gas for Si capable
of supplying silicon atoms (Si) together with a starting gas for introduction of hydrogen
atoms (H) or/and a starting gas for introduction of halogen atoms (X) into a deposition
chamber which can be brought to a reduced pressure to excite glow discharging within
said deposition chamber and form a layer comprising a polycrystalline silicon or a
layer comprising A-Si(
H,X) on the surface of a predetermined substrate which is previously placed at a predetermined
position. On the other hand, for formation according to the sputtering method, for
example, when sputtering a target constituted of Si in an atmosphere of an inert gas
such as Ar, He, etc., or a gas mixture based on these gases, the gas for introduation
of hydrogen atoms (H) or/and halogen atoms (X) may be introduced into the deposition
chamber for sputtering.
[0175] The substance which can be the starting material gas for Si supply to be used in
the present invention may include gaseous or gasifiable hydrogenated silicon (silanes)
such as SiH
4, Si
2H
6, Si
3H
8, Si
4H
10 and the like as effective ones, particularly preferably SiH
4, Si
2H
6 for easiness in handling during layer formation working, good Si supply efficiency,
etc.
[0176] As the effective starting gas for incorporation of halogen atoms to be used in the
present invention, there may be mentioned a number of halogen compounds such as halogen
gases, halides, interhalogen compounds and silane derivatives substituted with halogens
which are gaseous or gasifiable
[0177] Further, it is also effective in the present invention to use a gaseous or gasifiable
silicon compound containing halogen atoms which is constituted of both silicon atoms
and halogen atoms.
[0178] Typical examples of halogen compounds preferably used in the present invention may
include halogen gases such as of fluorine, chlorine, bromine or iodine and interhalogen
compounds such as BrF, ClF, ClF
3, BrF
5, BrF
3, IF
3, IF
7, ICl, IBr, etc.
[0179] As the silicon compound containing halogen atom, namely the so-called silane derivatives
substituted with halogen atoms, silicon halides such as SiF
4, Si
2F
6, SiCl
4, SiBr
4, or the like are preferred.
[0180] When the specific photoconductive member of this invention is formed according to
the glow discharge method by use of such a silicon compound containing halogen atoms,
it is possible to form a layer constituted of a polycrystalline silicon or A-Si:H
containing halogen atoms on a desired substrate without use of a hydrogenated silicon
gas as the starting gas capable of supplying Si.
[0181] In the case of preparing a layer containing halogen atoms according to the glow discharge
method, the basic procedure comprises introducing a silicon halide as the starting
material gas for Si supply together with a gas such as Ar, H
2, He, etc. at a predetermined mixing ratio and gas flow rates into a deposition chamber
for formation of a desired layer, and exciting glow discharge to form a plasma atmosphere
of these gases, whereby a desired layer can be formed on a desired substrate. For
effecting introduction of hydrogen atoms, a gas of a silicon compound containing hydrogen
atoms may be further mixed into these gases in a desired amount for layer formation.
[0182] The respective gases used are not limited only to single species, but a plural number
of gas species may be used at a desired mixing ratio.
[0183] For formation of a layer comprising polycrystalline silicon or A-Si(H,X) by the reactive
sputtering method or the ion-plating method, for example, a target of Si is used and
sputtering is effected thereon in a suitable gas plasma atmosphere in the case of
the sputtering method. Alternatively, in the case of ion-plating method, a polycrystalline
or single crystalline silicon is placed as vaporization source in a vapor deposition
boat, and the silicon vaporization source is vaporized by heating by resistance heating
method, electron beam method (EB method) or the like thereby to permit vaporized flying
substances to pass through a suitable gas plasma atmosphere.
[0184] During this procedure, in either of the sputtering method or the ion-plating method,
for introduction of halogen atoms into the layer formed, a gas of a halogen compound
as mentioned above or a silicon compound containing halogen as mentioned above may
be introduced into the deposition chamber to form a plasma atmosphere of said gas
therein.
[0185] When hydrogen atoms are to be introduced, a starting gas for introduction of hydrogen.atoms
such as H
2 and a gas such as silanes as mentioned above may be introduced into the deposition
chamber for sputtering, followed by formation of a plasma atmosphere of said gases.
[0186] In the present invention, as the starting gas for introduction of halogen atoms,
the halogen compounds or silicon compounds containing halogens as mentioned above
can effectively be used. In addition, it is also possible to use a gaseous or gasifiable
halide containing hydrogen atom as one of the constituents such as hydrogen halide,
including HF, HC1, HBr, HI and the like or halo-substituted hydrogenated silicon,
including SiH
2F
2, SiH
2I
2, SiH
2Cl
2, SiHCl
3, SiH
2Br
2, SiHBr
3 and the like as an effective starting material for formation of a charge injection
preventive layer and a photoconductive layer.
[0187] These halides containing hydrogen atom, which can introduce hydrogen atoms very effective
for controlling electrical or optical characteristics into the layer during formation
of the layer simultaneously with introduction of halogen atoms, can preferably be
used as the starting material for introduction of halogen atoms.
[0188] For incorporation of hydrogen atoms structurally into the layer-formed, in addition
to those as mentioned above, H
2 or a gas of hydrogenated silicon, including SiH
4, Si2H6, Si
3H
8, Si
4H
10 and so on may be permitted to be co-present with a silicon compound for supplying
Si in a deposition chamber, wherein discharging is excited.
[0189] For example, in the case of the reaction sputtering method, a Si target is used and
a gas for introduction of halogen atoms and H
2 gas are introduced together with, if necessary, an inert gas such as He, Ar, etc.
into a deposition chamber, wherein a plasma atmosphere is formed to effect sputtering
of said Si target, thereby forming a layer consisting of a polycrystalline silicon
or A-Si(H,X) on the substrate.
[0190] Further, there may also be introduced a gas such as of B
2H
6 or the like in order to effect also doping of impurities.
[0191] The amount of hydrogen atoms (H) or halogen atoms (X) incorporated in the charge
injection preventive layer 302, 402 in the light-receiving member for electrophotography
according to the present invention, or total amount of both of these atoms, may be
preferably 1 to 40 atomic %, more preferably 5 to 30 atomic %.
[0192] For controlling:the amounts of hydrogen atoms (H) and/or halogen atoms (X) in the
layer formed, the substrate temperature and/or the amounts of the starting materials
for incorporation of hydrogen atoms (H) or halogen atoms (X) to be introduced into
the deposition device system or the discharging power may be controlled.
[0193] For incorporating the group III atoms or the group V atoms, and the carbon atoms,
oxygen atoms or nitrogen atoms in the charge injection preventive layer 302, 402,
during formation of the charge injection preventive layer by glow discharge method
or sputtering method, the starting material for introduction of the group III atoms
or the group V atoms, and the starting material for introduction of oxygen atoms,
nitrogen atoms or carbon atoms may be used together with the starting material for
formation of the charge injection preventive layer as described above, while controlling
their amounts in the layer formed.
[0194] As such starting materials for introduction of carbon atoms, oxygen atoms and/or
nitrogen atoms, or the starting materials for introduction of the group III atoms
or the group V atoms, most of gaseous substances or gasified gasifiable substances
containing at least one of carbon atoms, oxygen atoms and nitrogen atoms, or the group
III atoms or the group V atoms may be employed.
[0195] For example, for incorporating oxygen atoms, a starting gas containing silicon atom
(Si) as the constituent atom, a starting gas containing oxygen atoms (O) as the constituent
atom and optionally a starting gas containing hydrogen atom (H) and/or halogen atom
(X) as the constituent atom may be used as a mixture with a desired mixing ratio.
Alternatively, a starting gas containing silicon atom (Si) as the constituent atom
and a starting gas containing oxygen atom (O) and hydrogen atom (H) as the constituent
atoms may be mixed also at a desired mixing ratio, or a starting gas containing silicon
atoms (Si) as the constituent atom and a starting gas containing the three of silicon
atom (Si), oxygen atom (O) and hydrogen atom (H) as the constituent atoms may be used
as a mixture.
[0196] As another method, a gas mixture comprising a starting gas containing silicon atom
(Si) and hydrogen atom (H) and a starting gas containing oxygen atom (O) may be also
employed.
[0197] As the starting gas for introduction of oxygen atoms and nitrogen atoms, there may
be included, for example, oxygen (O
2), ozone (O
3), nitrogen monooxide (NO), nitrogen dioxide (NO
2), dinitrogen monoxide (N
20), dinitrogen trioxide (N203), trinitrogen tetraoxide (N204), dinitrogen pentaoxide
(N
2O
5), nitrogen trioxide (NO
3), nitrogen (N
2), ammonia (NH
3), hydrogen azide (HN
3), hydrazine (NH
2NH
2). As the compound containing silicon (Si), oxygen (O) and hydrogen atom (H) as the
constituent atoms, there may be included lower siloxanes containing silicon atoms
(Si), oxygen atoms (O) and hydrogen atoms (H) such as disiloxane (H
3SiOSiH
3), trisiloxane (H
3SiOSiH
20SiH
3) and the like.
[0198] As carbon atom containing compounds for the starting material for introduction of
carbon atoms, there may be included, for example, saturated hydrocarbons having 1
to 4 carbon atoms, ethylenic hydrocarbons having 2 to 4 carbon atoms, acetylenic hydrocarbons
having 2 to 3 carbon atoms, etc.
[0199] More specifically, typical examples are saturated hydrocarbons such as methane (CH
4), ethane (C
2H
6), propane (C
3H
8), n-butane (n-C
4H
10), pentane (C
5H
12); ethylenic hydrocarbons such as ethylene (C
2H
4), propylene (C
3H
6), butene-1 (C
4H
8), butene-2 (C
4H
8), isobutylene (C
4H
8), pentene (C
5H
10); and acetylenic hydrocarbons such as acetylene (C
2H
2)
' methylacetylene (C
3H
4), butyne (C
4H
6) and the like.
[0200] Typical examples of the starting gas having Si, C and H as constituent atoms are
alkylsilanes such as Si(CH
3)
4, Si(C
2H
5)4 and the like.
[0201] When the glow discharge method is used for forming a charge injection preventive
layer containing the group III atoms or the group V atoms, the starting materials
which become the starting gases for formation of the layer comprise one selected suitably
from among the starting materials for formation of the charge injection preventive
layer constituted of polycrystaline silicon or A-Si(H,X) as mentioned above and a
starting material for introduction of the group III atoms or the group V atoms added
thereto. As such starting material for introduction of the group III atoms or the
group V atoms may be any of gaseous substances or gasified gasifiable substances containing
the group III atoms or the group V atoms as the constituent atom.
[0202] Specific examples of such starting materials for introduction of the group III atoms
may include those for introduction of boron atoms such as hydrogenated boron, including
B
2H6, B
4H
10, B
5H
9, B
5H
10, B
6H
10,
B6H12' B6H
14 and the like, halogenated boron such as BF3, BC1
2, BBr
3 and the like. Otherwise, AlCl
3, GaCl
3, InCl
3, TlCl
3 may be also employed.
[0203] The starting material for introduction of the group V atoms which can be effectively
used in the present invention may include hydrogenated phosphorus such as PH
3, P
2H
4 and the like; halogenated phosphorus such as PH
4I, PF
3, PF
5, PCl
3, PCl
5, PBr
3, PBr
5, PI
3 and the like for introduction of phosphorus atoms. Otherwise, AsH
3, AsF
3, AsCl
3, AsBr
3, AsF
5,
SbH
3, SbF
3, SbF
5, SbCl
3; SbCl
5,
BiH3,
BiCl3, BiBr
3, etc. may be also employed-as effective starting materials for introduction of the
group V atoms.
[0204] The content of the group III atoms or the group V atoms in the charge injection preventive
layer containing the group III atoms or the group V atoms can be controlled freely
by controlling the gas flow rates, the gas flow rate ratios of the starting materials
for introduction of the group III atoms or the group V atoms, the discharging power,
the substrate temperature and the pressure in the deposition chamber, etc.
[0205] The substrate temperature for the purpose of accomplishing effectively the objects
of the present invention should be selected suitably within the optimum range. When
a charge injection preventive layer 302, 402 consisting of A-Si(H,X) is formed, it
should be generally 50 to 350°C, preferably 100 to 300°C. When a charge injection
preventive layer is formed of polycrystalline silicon, it should be generally 200°C
to 700°C, preferably 250°C to 600°C.
[0206] For formation of the charge injection preventive layer in the present invention,
it is desirable to employ the glow discharge method or the sputtering method for the
reasons such as relatively easier severe control of the composition ratio of the atoms
constituting the layer or control of the layer thickness, and in the case of forming
a charge injection preventive layer according to these layer forming methods, discharging
power or gas pressure during layer formation is also one of important factors influencing
the characteristic of the charge injection preventive layer to be prepared similarly
as the above substrate temperature.
[0207] The discharging power condition for preparing effectively the charge injection preventive
layer having the characteristics for accomplished the objects in the present invention
with good productivity and efficiency may be generally 1100 to 5000 W, preferably
1500 to 4000 W for the substrate temperature (Ts) of 200 to 350°C and generally 100
to 5000 W, preferably 200 to 4000 W for the substrate temperature of 350 to 700°C,
in the case of forming a charge injection preventive layer constituted of polycrystalline
silicon, or generally 10 to 1000 W, preferably 20 to 500 W in the case of forming
a charge injection preventive layer constituted of A-Si(H,X). The gas pressure within
the deposition chamber may be 10
-3 to 0.8 Torr, preferably 5 x 10
-3 to 0.5 Torr in the case of forming a charge injection preventive layer constituted
of polycrystalline silicon or 0.01 to 1 Torr, preferably 0.1 to 0.5 Torr in the case
of forming a charge injection pre-: ventive layer of A-Si(H,X).
[0208] In the present invention, the numerical value ranges desirable for the substrate
temperature, discharging power for preparing a charge injection preventive layer may
be the values within the ranges as mentioned above, but these layer forming factors
are not determined independently and separately, but it is desirable that the optimum
values for the factors for forming respective layers should be determined based on
the mutual organic relationship so that a charge injection preventive layer with desired
characteristics may be formed.
[0209] Fig. IE and Fig. 1F illustrate schematically the fifth and sixth preferred embodiments
of the light-receiving member for electrophotography of the present invention.
[0210] The light-receiving member for electrophotography shown in Fig. lE and Fig. 1F has
a light-receiving layer 500, 600 on the substrate 501, 601 on the substrate for light-receiving
member, said light-receiving layer 500, 600 comprising a longer wavelength light absorbing
layer 507, 607, a charge injection preventive layer 502, 602, a photoconductive layer
503, 603 comprising A-Si(H,X) and having photoconductivity, and surface layer 504,
604. 606 shows an adhesion layer.
[0211] The light-receiving member 500, 600 shown in Fig. lE and 1F corresponds to the light-receiving
member for electrophotography 300, 400 shown in Fig. 1C, 1D and, except for having
a longer wavelength light absorbing layer (IR layer) 507, 607, the light-receiving
member for electrophotography 500 shown in Fig. 1E is entirely the same as the light-receiving
member for electrophotography 300 shown in Fig. lC, and the light-receiving member
for electrophotography 600 shown in Fig. 1F as the light-receiving member for electrophotography
400 shown in Fig. 1D.
[0212] Accordingly, description except for the longer wavelength light absorbing layer 507,
607 is omitted below.
Longer Wavelength Absorbing Layer
[0213] The longer wavelength absorbing layer 507,607 in the present invention is constituted
of an inorganic material containing silicon atoms and germanium atoms (polycrystalline
material or amorphous material), and the germanium atoms contained in said layer may
be contained uniformly throughout the layer, or alternatively may be contained throughout
the layer but with nonuniform distributed concentration in the layer thickness direction.
However, in either case, it is required also for uniformization of the characteristics
in the interplanar direction that they should be contained throughout the layer with
uniform distribution in the interplanar direction in parallel to the surface of the
substrate. That is, the germanium atoms may be contained throughout the layer thickness
direction in the longer wavelength absorbing layer 507,607 and in the state enriched
toward the above substrate side opposite to the side (the free surface side of the
light-receiving layer) where the above substrate is provided, or in the distribution
state opposited thereto. ] ;
[0214] In the light-receiving member of the present invention, the distribution state of
germanium atoms contained in the longer wavelength absorbing layer 507,607 as mentioned
above should desirably take the distribution state as mentioned above in the layer
thickness direction, while a uniform distribution state in the interplanar direction
in parallel to the surface of the substrate.
[0215] Also, in one preferred embodiment, the distribution state of germanium atoms in the
longer wavelength absorbing layer 507,607 is such that germanium atoms are distributed
continuously throughout the whole layer region and the distributed concentration C
in the layer thickness direction is given a change in which it is reduced from the
substrate side toward the charge injection preventive layer, and therefore affinity
between the longer wavelength absorbing layer 507,607 and the charge injection preventive
layer 502,602 is excellent, and also by making extremely greater the distributed concentration
C of germanium atoms at the end portion on the substrate side as described later,
the light on the wavelength side which cannot substantially be absorbed by the photoconductive
layer 503, 603 can be absorbed substantially completely by the longer wavelength absorbing
layer, whereby interference by reflection from the substrate surface can be prevented.
[0216] Figs. 22 through 27 show typical examples when the distribution state in the layer
thickness direction of germanium atoms contained in the longer wavelength absorbing
layer 507, 607 of the light-receiving member in the present invention is nonuniform.
[0217] In Figs. 22 through 27, the axis of abscissa indicates the distributed concentration
C of germanium atoms, and the axis of ordinate the layer thickness of the longer wavelength
absorbing layer, t
B showing the position of the end face of the longer wavelength absorbing layer 507,
607 on the substrate side, t the position of the end face of the longer wavelength
absorbing layer 507, 607 on the opposite side to the substrate side. That is, the
longer wavelength absorbing layer containing germanium atoms is formed from the t
B side toward the t
T side.
[0218] Fig. 22 shows a first typical example of the distribution in the layer thickness
direction of germanium atoms contained in the longer wavelength absorbing-layer.
[0219] In the example shown in Fig. 22, from the interface position t
B where the surface on which the longer wavelength absorbing layer 507, 607 containing
germanium atoms is formed contacts the surface of said longer wavelength absorbing
layer 507, 607 to the position t
8, germanium atoms are contained in the longer wavelength absorbing layer 507, 607
formed while the distributed concentration C of germanium atoms taking a constant
value of C
46, and the concentration is reduced gradually and continuously from the concentration
C
2 from the position t
1 to the interface position t . At the interface position t
T, the distributed concentration C of germanium atoms is made C
48.
[0220] In the example shown in Fig. 23, the distributed concentration C of germanium atoms
contained is reduced from the concentration C
49 gradually and continuously from the position t
B to the position t
T, until it becomes the concentration C
50 at the position t
T.
[0221] In the case of Fig. 24, the distributed concentration C of germanium atoms is made
a constant value of C
51 from the position t
B to the position t
9, and reduced gradually and continuously between the position t
9 and the position t
T, until the distributed concentration C is made substantially zero at the position
t
T (here, substantially zero means the case-of less than detectable limit of amount).
[0222] In the case of Fig. 25, the distributed concentration C of germanium atoms is reduced
from the concentration C
53 continuously and gradually from the position t
B to the position t
T, until it is made substantially zero at the position t
T.
[0223] In the example shown in Fig. 26, the distributed concentration C of germanium atoms
is constantly a value of C
54 between the position t
B and the position t
10, and is made a concentration C
55 at the position tT. Between the positions t
10 and t
T, the distributed concentration C is reduced as a first order function from the position
t
10 to the position t
T.
[0224] In the example shown in Fig. 27, the distributed concentration C of germanium atoms
is reduced from the concentration C
56 to substantially zero as a first order function from the position t
B to the position
tT.
[0225] As described above about some typical examples of distribution state in the layer
thickness direction of germanium atoms contained in the longer wavelength absorbing
layer by referring to Figs. 22 through 27, in the present invention, the case of providing
a distribution state of germanium atoms having a portion of, higher distributed concentration
C of germanium atoms on the substrate side and-having a portion of the above distributed
concentration C which has been made considerably made lower as compared with the substrate
side on the interface t
T side may be mentioned as a preferable example. As the distribution state in the layer
thickness direction of germanium atoms, it is desirably that the layer formation should
be effected so that the maximum value Cmax of the distributed concentration of germanium
atoms should preferably be 1000 atomic ppm or more, more preferably 5000 atomic ppm
or more, optimally 1 x 10
4 atomic ppm or more, based on the sum with silicon atoms.
[0226] In the present invention, the content of germanium atoms contained in the longer
wavelength absorbing layer 507, 607 may be determined as desired so as to accomplish
effectively the objects of the present invention, but may be preferably 1 to 10 x
10 atomic ppm, more preferably 100 to 9.5 x 10
5 atomic ppm, optimally 500 to 8 x 10
S atomic ppm, based on the sum with silicon atoms.
[0227] The above-mentioned longer wavelength absorbing layer 507, 607 may also contain at
least one of substances for controlling conductivity (valence electron controller),
oxygen atoms, nitrogen atoms and carbon atoms.
[0228] As the substance for controlling conductivity to be contained in the charge injection
preventive layer 102, there may.be mentioned such impurities in the field of semiconductors
as described in the explanation of the charge injection preventive layer 302, 402.
[0229] In the present invention, the content of the substance for controlling conductivity
characteristic to be contained in the longer wavelength absorbing layer 507, 607 may
be preferably 0.01 to 5 x 1
05 atomic ppm, more preferably 0.5 to 1 x 10
4 atomic ppm, optimally 1 to 5 x 10
3 atomic ppm.
[0230] The content of nitrogen atoms (N), oxygen atoms (0), carbon atoms (C) or the sum
of the contents of two or more of these in the longer wavelength absorbing layer 507,
607 may be preferably 0.01 to 40 atomic %, more preferably 0.05 to 30 atomic %, optimally
0.1 to 25 atomic %.
[0231] In the present invention, the layer thickness of the longer wavelength absorbing
layer 507, 607 0 0 may preferably be 30 A to 50 pm, more preferably 40 A 0 to 40 µm,
optimally 50 A to 30 µm.
[0232] In the present invention, typical examples of halogen atoms (X) to be incorporated
in the longer wavelength light absorbing layer 507, 607 are F, Cl, Br, I, especially
preferably F and Cl.
[0233] In the present invention, formation of the longer wavelength light absorbing layer
507, 607 may be conducted according to the vacuum deposition method utilizing-discharging
phenomenon, such as glow discharge method; sputtering method or ion-plating method.
[0234] For example, for formation of the longer wavelength absorbing layer 507, 607 constituted
of a polycrystalline or amorphous material containing silicon atoms and germanium
atoms according to the glow discharge method, the basic procedure comprises introducing
a starting gas for Si supply capable of supplying silicon atoms (Si) and a starting
gas for Ge supply capable of supplying germanium atoms (Ge), optionally together with
a starting gas for introduction of hydrogen atoms (H) or/and a starting gas for introduction
of halogen atoms (X) into a deposition chamber which can be internally brought to
a reduced pressure to excite glow discharging within said deposition chamber and form
a layer on the surface of a predetermined substrate which is previously placed at
a predetermined position. On the other hand, for formation according to the sputtering
method, a target constituted of Si or two sheets of said target and a target constituted
of Ge, or a target of a mixture of Si and Ge may be used in an atmosphere such as
of an inert gas of Ar, He, etc. or a gas mixture based on these gases, and a starting
gas for Ge supply optionally diluted with a diluting gas such as He, Ar, etc. is introduced,
optionally together with a gas for introduction of hydrogen atoms (H) or/and halogen
atoms (X), into the deposition chamber for sputtering and form a plasma atmosphere
of desired gases.
[0235] The substance which can be the starting material gas for Si supply to be used in
the present; invention may include gaseous or gasifiable hydrogenated silicon (silanes)
such as SiH
4, Si
2H
6, Si
3H
8, Si
4H
10and the like as effective ones, particularly preferably SiH
4, Si
2H
6 for easiness in handling during layer formation working, good Si supply efficiency,
etc.
[0236] The substance which can be the staring material gas for Ge supply may include gaseous
or gasifiable hydrogenated germanium such as GeH
4, Ge
2H
6, Ge
3H
8, Ge
4H
10, Ge
5H
12, Ge
6H
14, Ge
7H
16, Ge
8H
18,
Ge9H20 and the like as effective ones, particularly preferably GeH
4, Ge
2H
6, Ge
3H
8 for easiness in handling during layer formation working, good Ge supply efficiency,
etc.
[0237] As the effective starting gas for incorporation of halogen atoms to be used in the
present invention, there may be mentioned a number of halogen compounds such as halogen
gases, halides, interhalogen compounds and silane derivatives substituted with halogens
which are gaseous of gasifiable.
[0238] Further, it is also effective in the present invention to use a gaseous or gasifiable
silicon compound containing halogen atoms which is constituted of both silicon atoms
and halogen atoms.
[0239] Typical examples of halogen compounds preferably used in the present invention may
include halogen gases such as of fluorine, chlorine, bromine or iodine and interhalogen
compounds such as BrF, ClF, CIF
3, BrF
5, BrF
3, IF
3, IF
7, IC1, IBr, etc.
[0240] As the silicon compound containing halogen atom, namely the so-called silane derivatives
substituted with halogen atoms, silicon halides such as SiF
4, Si
2F
6, SiCl4, SiBr
4, or the like are preferred.
[0241] When the specific light-receiving member of this invention is formed according to
the glow discharge method by use of such a silicon compound containing halogen atoms,
it is possible to form a layer constituted of A-Si:H containing halogen atoms on a
desired substrate without use of a hydrogenated silicon gas as the starting gas capable
of supplying Si.
[0242] In the case of preparing a layer containing halogen atoms according to the glow discharge
method, the basic procedure comprises introducing a silicon halide as the starting
material gas for Si supply together with a gas such as Ar, H
2, He, etc. at a predetermined mixing ratio and gas flow rates into a deposition chamber
for formation of a layer, and exciting glow discharge to form a plasma atmosphere
of these gases, whereby a desired layer can be formed on a desired substrate. For
effecting introduction of hydrogen atoms, a gas of a silicon compound containing hydrogen
atoms may be further mixed into these gases in a desired amount for layer formation.
[0243] In the case of forming a longer wavelength light absorbing layer 507, 607, as the
starting gas for introduction of halogen atoms, the halogen compounds or silicon compounds
containing halogens as mentioned above can effectively be used. In addition, it is
also possible to use a gaseous or gasifiable substance such as halides containing
hydrogen atom as one constituent, for example, hydrogenated germanium halide such
as GeHF
3, GeH2F2, GeH
3F, GeHCl
3, GeH
2Cl
2, GeH
3Cl, GeHBr
3, GeH2Br2, GeH
2Br, GeHI
2, GeH
2I
2, GeH
3I and the like; and halogenated germanium such as GeF
4, GeCl
4, GeBr
4, GeI
4, GeF
2, GeCl
2, GeBr
2, GeI
2 and the like as an effective starting material for formation of a longer wavelength
light absorbing layer.
[0244] The respective gases used are not limited only to single species, but a plural number
of gas species may be used at a desired mixing ratio.
[0245] For formation of a layer comprising A-Si(H,X) by the reactive sputtering method or
the ion-plating- method, for example, a target of Si is used and sputtering is effected
thereon in a suitable gas plasma atmosphere in the case of the sputtering method.
Alternatively, in the case of ion-plating method, a polycrystalline or single crystalline
silicon is placed as vaporization source in a vapor deposition boat, and the silicon
vaporization source is vaporized by heating by resistance heating method or electron
beam method (EB method) thereby to permit vaporized flying substances to pass through
a suitable gas plasma atmosphere.
[0246] During this procedure, in both of the sputtering method and the ion-plating method,
for introduction of halogen atoms into the layer formed, a gas of a halogen compound
as mentioned above or a silicon compound containing halogen as mentioned above may
be introduced into the deposition chamber to form a plasma atmosphere of said gas
therein.
[0247] When hydrogen atoms are to be introduced, a starting gas for,introduction of hydrogen
atoms such as H
2 and a gas such as silanes as mentioned above may be introduced into the deposition
chamber for sputtering, followed by formation of a plasma atmosphere of said gases.
[0248] In the present invention, as the starting gas for introduction of halogen atoms,
the halogen compounds or silicon compounds containing-halogens or germanium compounds
containing halogens as mentioned above can effectively be used. In addition, it is
also possible to use a gaseous or gasifiable halide containing hydrogen atom as one
of the constituents such as hydrogen halide, including HF, HC1, HBr, HI and the like
or halo-substituted hydrogenated silicon, including SiH
2F
2' Si
H2I2' SiH
2Cl
2, SiHCl
3, SiH
2Br
2, SiHBr
3and the like as an effective starting material for formation of a longer wavelength
light absorbing layer.
[0249] These halides containing hydrogen atom, which can introduce hydrogen atoms very effective
for controlling electrical or optical characteristics into the layer during formation
of the layer simultaneously with introduction of halogen atoms, can preferably be
used as the starting material for introduction of halogen atoms.
[0250] For incorporation of hydrogen atoms structurally into the layer formed, in addition
to those as mentioned above,-H
2 or a gas of hydrogenated silicon, including SiH
4, Si
2H
6, Si
3H
8, Si
4H
10 and so on may be permitted to be co-present with a silicon compound for supplying
Si in a deposition chamber, wherein discharging is excited.
[0251] For example, in the case of the reactive sputtering method, a Si target is used and
a gas for introduction of halogen atoms and H
2 gas are introduced tagether with, if necessary, an inert gas such as He, Ar, etc.
into a deposition chamber, wherein a plasma atmosphere is formed to effect sputtering
of said Si target, thereby forming a layer of A-Si(H,X) on the substrate.
[0252] Further, there may also be introduced a gas such as of B
2H
6 or others in order to effect also doping of impurities.
[0253] The amount of hydrogen atoms (H) or halogen atoms (X) incorporated in the longer
wavelength light absorbing layer in the light-receiving member for electrophotography
according to the present invention, or total amount of both of these atoms, may be
preferably 0.01 to 40 atomic %, more preferably 0.05 to 30 atomic %, optimally 0.1
to 25 atomic %.
[0254] For controlling the amounts of hydrogen atoms (H) or/and halogen atoms (X) in the
layer formed, the substrate temperature or/and the amounts of the starting materials
for incorporation of hydrogen atoms (H) or halogen atoms (X) to be introduced into
the deposition device system or the discharging power may be controlled.
[0255] For incorporating the group III atoms or the group V atoms, and the carbon atoms,
oxygen atoms or nitrogen atoms in the longer wavelength light absorbing layer 507,
607, during formation of the longer wavelength light absorbing layer 507, 607, by
glow discharge or reactive sputtering method, the starting material for introduction
of the group III atoms or the group V atoms, and the starting material for introduction
of oxygen atoms, nitrogen atoms or carbon atoms may be used together with the starting
material for formation of the longer wavelength light absorbing layer as described
above, while controlling their amounts in the layer formed.
[0256] As such starting materials for introduction of carbon atoms, oxygen atoms or/and
nitrogen atoms, or the starting materials for introduction of the group III atoms
or the group V atoms, most of gaseous substances or gasified or gasifiable substances
containing at least one of carbon atoms, oxygen atoms and nitrogen atoms, or the group
III atoms or the group V atoms may be employed.
[0257] For example, for incorporating oxygen atoms, a starting gas containing silicon atom
(Si) as the constituent atom, a starting gas containing oxygen atoms (O) as the-constituent
atom and optionally a starting gas containing hydrogen atom or/and halogen atom.(X)
as the constituent atom may be used as a mixture with a desired mixing ratio. Alternatively,
a starting gas containing silicon atom (Si) as the constituent and a starting gas
containing oxygen atom (O) and hydrogen atom (H) as the constituent atoms may be mixed
also at a desired mixing ratio, or a starting gas containing silicon atom (Si) as
the constituent atom and a starting gas containing the three of silicon atom (Si),
oxygen atom (O) and hydrogen atom (
H) as the constituent atoms may be used as a mixture.
[0258] As another method, a gas mixture comprising a starting gas containing silicon atom
(Si) and hydrogen atom (H) and a starting gas containing oxygen atom (O) may be also
employed.
[0259] As the starting gas for introduction of oxygen atoms and nitrogen atoms, there may
be included, for example, oxygen (O
2), ozone (O
3), nitrogen monooxide (NO), nitrogen dioxide (NO
2), dinitrogen monooxide (N
20), dinitrogen trioxide (N
20
3), dinitrogen tetraoxide (N
2O
4), dinitrogen pentaoxide (N
2O
5) , nitrogen trioxide (NO
3), nitrogen (N
2), ammonia (NH
3), hydrogen azide (HN
3), hydrazine (NH
2NH
2). As the compound containing silicon (Si), oxygen (O) and hydrogen atom (H) as the
constituent atoms, there may be included lower siloxanes such as disiloxame (H
3SiOSiH
3) , trisiloxane (H
3SiOSiH
20SiH
3) and the like.
[0260] As carbon atom containing compounds for the starting material for introduction of
carbon atoms, there may be included, for example, saturated hydrocarbons having 1
to 4 carbon atoms, ethylenic hydrocarbons having 2 to 4 cartons,lacetylenic hydrocarbons
having 2 to 3 carbon atoms, etc.
[0261] More specifically, typical examples are saturated hydrocarbons such as methane (CH
4), ethane (C
2H
6) propane (C
3H
8) , n-butane (n-C
4H
10), pentane (
C5H12); ethylenic hydrocarbons such as ethylene (C
2H
4), propylene (C3H6) butene-1 (C
4H
8) , butene-2 (C
4H
8), isobutylene (C
4H
8),
pen
tene (C
5H
10); and acetylenic hydrocarbons such as acetylene (C2H2), methylacetylene (C
3H
4), butyne (C
4H
6) and the like.
[0262] Typical examples of the starting gas having Si, C and H as constituent atoms are
alkylsilicides such as Si(CH
3)
4, Si(C
2H
5)
4 and the like.
[0263] When the glow discharge method is used for forming a longer wavelength light absorbing
layer 507, 607 containing the group III atoms or the group V atoms, the starting materials
which become the starting gases for formation of said layer comprise one selected
suitably from among the starting materials for formation of the longer wavelength
light absorbing layer 507, 607 and a starting material for introduction of the group
III atoms or the group V atoms added thereto. As such starting material for introduction
of the group III atoms or the group V atoms may be any of gaseous substances or gasified
gasifiable substances containing the group III atoms or the group V atoms as the constituent
atom.
[0264] Specific examples of such starting materials for introduction of the group III atoms
may include those for introduction of boron atoms such as hydro--g
enated boron, including H
2H
6, B
4H
10' B
5H
9,B
5H
10' B
6H
10, B
6H
12,
B6H14 and the like, halogenated boron such as BF
3, BC1
2, BBr
3 and the like. Otherwise, AlCl
3, GaCl
3, InCl
2, TiCl
3, etc., may be. also employed.
[0265] The starting material for introduction of the group V atoms which can be effectively
used in the present invention may include hydrogenated phosphorus such as PH
3, P
2H
4 and the like; halogenated phosphorus such as PH
4I, PF
3, PF
5, PCl
3 PCl
5, PBr
3, PBr
5, PI
3 and the like for introduction of phosphorus atoms. Otherwise, AsH3, AsF
3, AsCl
3, AsBr
3, AsF
5, SbH
3, SbF
3, SbF
5, SbCl
3, SbCl
5, BiH
3,BiCl
3, BiBr
3, etc. may be also employed as effective starting materials for introduction of the
group V atoms.
[0266] The content of the group III atoms or the group V atoms in the longer wavelength
light absorbing layer 507, 607 containing the group III atoms or the group V atoms
can be controlled desirably by controlling the gas flow rates, the gas flow rate ratios
of the starting materials for introduction of the group III atoms or the group V atoms,
the discharging power, the substrate temperature and the pressure in the deposition
chamber, etc.
[0267] The substrate temperature for the purpose of accomplishing effectively the objects
of the present invention should be selected suitably within the optimum range. When
a longer wavelength_light absorbing layer 507,607 is formed of a polycrystalline material,
it should preferably 200 to 700°C, more preferably 250 to 600°C. When a longer wavelength
light absorbing layer is formed of an amorphous material, it should preferably 50°C
to 350°C, more preferably 100°C to 300°C.
[0268] For formation of the longer wavelength light absorbing layer 507, 607, it is desirable
to employ the glow discharge method or the sputtering method for the reasons such
as relatively easiness in delicate control of the composition ratio of the atoms constituting
the layer or of the layer thickness compared to other methods, and in the case of
forming a longer wavelength light absorbing layer 507, 607 according to these layer
forming methods, discharging power or gas pressure during layer formation is also
one of important factors influencing the characteristic of the longer wavelength light
absorbing layer 507, 607 to be prepared similarly as the above substrate temperature.
[0269] The discharging power condition for preparing effectively the longer wavelength light
absorbing layer 507, 607 having the characteristics for accomplishing the objects
in the present invention with good productivity and efficiency may be preferably 100
to 5000 W, more preferably 200 to 2000-
W, in the case of forming a longer wavelength light absorbing layer 507, 607 constituted
of a polycrystalline material, or preferably 10 to 1000 W, more preferably 20 to 500
W in the case of forming a longer wavelength light absorbing layer 507, 607 constituted
of an amorphous material. The gas pressure within the deposition chamber may be preferably
10
-3 to 0.8 Torr, more preferably 5 x 10
-3 to 0.5 Torr in the case of forming a longer wavelength light absorbing , layer 507,
607 constituted of a polycrystalline material, or preferably 0.01 to 1 Torr, more
preferably 0.1 to 0.5 Torr in the case of forming a longer wavelength light absorbing
layer 507, 607 constituted of an amorphous material.
[0270] In the present invention, desirable numerical value ranges of substrate temperature
and discharging power for preparing a longer wavelength light absorbing layer 507,
607 may be the values within the ranges as mentioned above, but these layer forming
factors are not determined independently and separately, but it is desirable that
the optimum values for the factors for forming respective layers should be determined
based on the mutual organic relationship so that a longer wavelength light absorbing
layer 507, 607 with desired characteristics may be formed.
[0271] Fig. lG and Fig. 1H show the seventh and the eighth examples of the preferred embodiments
of the light-receiving member for electrophotography of the present invention.
[0272] The respective layer constitutions of the light-receiving members for electrophotography
shown in Fig. 1G and Fig. 1H are the same as the respective light-receiving members
shown in Fig. 1C and Fig. 1D except that the longer wavelength light absorbing layers
(IR layers) 707, 807 posessed by the light-receiving members for electrophotography
shown in Fig. lE and Fig. 1F are provided in place of the charge injection preventive
layers 302, 402 posessed by the light-receiving members for electrophotography shown
in Fig. 1C and Fig. 1D:
[0273] The respective light-receiving members for electrophotography shown in Fig. 1G and
Fig. 1H can absorb effectively the longer wavelength light effectively by providing
longer wavelength light absorbing layers 707, 807 between the substrates 701, 801
and the photoconductive layers 703, 803, whereby interference when using a coherent
light such as laser beam can be effectively prevented.
[0274] Fig. 28 through Fig. 32 respectively show examples of light-receiving members for
electrophotography having light-receiving layers with the same layer constitutions
as the light-receiving members for electrophotography shown in Figs. 1C through 1G
. on the same substrate as the substr.ate-1501 of the light-receiving-member for electrophotography
1500 shown in Fi
g. 3.
[0275] That is, in Figs. 28 through 32, 900, 1000, 1100, 1200, and 1300 represent light-receiving
layers, 901, 1001, 1101, 1201, and 1301 substrates, 902, 1002, 1102, and 1202 charge
injection preventive layers, 903, 1003, 1103, 1203, and 1303 photoconductive layers,
904, 1004, 1104, 1204, and 1304 surface layers, 905, 1005, 1105, 1205, and 1305 free
surfaces, 906 and 1206 adhesion layers, 1107, 1207, and 1307 longer wavelength light
absorbing layers, respectively.
[0276] Next, the method for forming the light-receiving member is outlined below.
[0277] Fig. 33 shows an example of the apparatus for preparation of the light-receiving
member for electrophotography.
[0278] The gas bombs 3302 through 3306 in the Figure are hermetically filled with the starting
gases for formation of the-respective layers of the present invention. For example,
3302 is a SiH
4 gas (purity 99.999%) bomb, 3303 a B
2H
6 gas diluted with H
2 (purity 99.999 %, hereinafter abbreviated as B
2H
6/H
2) bomb, 3304 a H
2 gas (purity 99.99999 %) bomb, 3305 a NO gas (purity 99.999 %) bomb, and 3306 a CH
4 gas (purity 99.99 %) bomb.
[0279] For permitting these gases to flow into the reaction chamber 3301, on confirmation
that the valves 3322 to 3326 of the gas bombs 3302 to 3306 and the leak valve 3335
are closed, and also on confirmation that the inflow valves 3312 to 3316, the outflow
valves 3317 to 3321, and the auxiliary valves 3332 to 3333 are opened, first the main
valve 3334 is opened to evacuated the reaction chamber 3301 and the gas pipelines.
Next, when the reading on the vacuum gauge 3336 becomes about 5 x 10
-6 Torr, the auxiliary valves 3332 to 3333 and the outflow valves 3317 to 3312 are closed.
[0280] Referring to an example when a light-receiving member for electrophotography with
a layer constitution shown in Fig. 1F is formed on the substrate cylinder 3337, SiH
4 gas from the gas bomb 3302, H
2 gas from the gas bomb 3304, B
2H
6/H
2 gas from the gas bomb 3303, and NO gas from the gas bomb 3305 are permitted to flow
into the mass flow controllers 3307 to 3310 by opening the valves 3322 through 3325
to control the pressures at the outlet pressure gauges 3327 to 3330 to 1
Kg/cm
2 and opening gradually the inflow valves 3312 to 3315. Subsequently, by opening gradually
the outflow valves 3317 to 3320 and the auxiliary valve 3332, the respective gases
are permitted to flow into the reaction chamber 3301. During this operation, the outflow
valves 3317 to 3320 are controlled so that the ratio of SiH
4 gas flow rate, B
2H
6/He gas flow rate, and NO gas flow rate may become a desired value and also the - opening
of the main valve 3334 is controlled while seeing the reading on the vacuum gauge
3336 so that the pressure=within the reaction chamber may become a desired value.
And, after the temperature of the substrate cylinder 3337 is confirmed to be set at
a temperature of 50 to 350°C by the heater 3338, the power 3340 is set at a desired
power to excite glow discharging within the reaction chamber 3301 and at the same
time the operation of changing gradually the valve 3318 or/and 3320 manually or by
use of an externally driven motor to change the flow rate of B
2H
6/H
2 gas or/and NO gas following the change rate curve previously designed,thereby controlling
the distributed concentration of boron atoms or/and oxygen atoms in the layer thickness
direction contained in the layer formed.
[0281] At the point when a charge injection preventive layer containing boron atoms and
oxygen atoms to a desired thickness is formed, the outflow valves 3320 and 3318 are
closed, with shut-down of inflow of B
2H
6/He gas and NO gas, and at the same time with control of flow rates of SiH
4 gas and H
2 gas by controlling the outflow valves 3317 and 3319, layer formation is subsequently
performed, thereby forming a photoconductive layer containing none of oxygen atoms
and boron atoms on the charge injection preventive layer to a desired thickness.
[0282] Also, when a photoconductive layer containing oxygen atoms or/and boron atoms is
formed, the outflow valves 3318 or/and 3320 may be controlled to desired flow rates
in place of being closed.
[0283] When halogen atoms are contained in the charge injection preventive layer and the
photoconductive layer, for example, SiF
4 gas in further added to the above gases to be delivered into the reaction chamber
3301.
[0284] In formation of the respective layers, depending on the selection of the gas species,
the layer forming speed can be enhanced. For example, when layer formation is performed
by use of Si
2H
6 gas in place of SiH
4 gas, the speed can be enhanced by several times to improve productivity.
[0285] For formation of the surface layer on the photoconductive layer as prepared above,
according to the same valve operations as in the case of forming the photoconductive
layer, for example, SiH
4 gas, CH
4 gas, and optionally a diluting gas such as H
2, etc., may be flowed at desired flow rate ratio into the reaction chamber 3301, followed
by excitation of glow discharging following desired conditions.
[0286] The content of carbon atoms contained in the surface layer can be controlled as desired
by varying freely the flow rate ratio of SiH
4 gas and CH
4 gas introduced into the reaction chamber 3301 as desired.
[0287] Also, the content of hydrogen atoms contained in the surface layer can be controlled
by, for example, varying freely the flow rate of H
2 gas introduced into the reaction chamber 3301 as desired.
[0288] All of the outflow valves other than those for necessary gases during formation of
the respective layer are closed as a matter of course and also, in order to avoid
remaining of the gases employed for formation of the previous layer during formation
of each layer in the reaction chamber 3301, and in the pipelines from the outflow
valves 3317 to 3321 to the reaction chamber 3301, the operation of evacuating internally
the system once to high vacuum by closing of the outflow valves 3317 to 3321 and full
opening of the main valve 3334 by opening of the auxiliary valve 3332 is practiced,
if necessary.
[0289] Also, during layer formation, in order to effect uniformization, the substrate cylinder
3337 may be also rotated at a desired constant speed by a motor 3339.
Example lA
[0290] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table lA. The light-receiving member (hereinafter expressed
as drum) was set on an electrophotographic device, and, under various conditions,
electrophotographic characteristics such as initial charging ability, residual potential,
ghost, etc., were checked, and also lowering in charging ability, sensitivity deterioration
and increase of image defects after successive copying of 1,500,000 sheets were examined.
Further, the image flow of the drum in an atmosphere of high temperature and high
humidity of 35°C and 85 % was also evaluated. And, the drum completed of evaluation
was cut out at the portions corresponding to the upper, middle and lower portions
of the image portion to prepare a samples, which were provided for quantitative analysis
of hydrogen contained in the surface layer by utilization of SIMS, and also the component
profiles in the layer thickness direction of silicon atoms (Si), carbon atoms (C)
and hydrogen atoms (H) in the surface layer were examined. The above evaluation results
and the maximum value of the hydrogen content in the surface layer are shown in Table
2A, and the above component profiles are shown in Table 34. As shown in Table 2A,
remarkable superiority was observed in the respective items particularly of initial
charging ability, image flow,residual potential, ghost and photosensitive irregularity
in the axial direction, sensitivity deterioration.
;
Comparative example lA
[0291] Except for changing the preparation con- ditions as shown in Table 3A, the drum and
samples for analysis were prepared by the same device and method as in Example 1A
and provided for the same evaluation and analysis. The results are shown in Table
4A.
[0292] As can be seen from Table 4A, it was recognized that the respective items were inferior
as compared with Example 1A.
Example 2A, Comparative example 2A
[0293] The preparation conditions of the surface layer were changed variously as shown in
Table 5A, with other conditions being the same as in Example lA, to prepare a plural
number of drums and samples for analysis. These drums and samples were evaluated and
analyzed similarly as in Example lA to obtain the results as shown in Table 6A.
Example 3A
[0294] The preparation conditions of the photoconductive layer were changed variously as
shown in Table 7A, with other conditions being the same as in Example lA, to prepare
a plural number of drums. These drums were evaluated similarly as in Example lA to
obtain the results as shown in Table 8A.
Example 4A
[0295] The preparation conditions of the photoconductive layer were changed variously as
shown in Table 9A, with other conditions being the same as in Example lA, to prepare
a plural number of drums. These drums were evaluated similarly as in Example 1A to
obtain the results as shown in Table 10A.
Example 5A
[0296] On substrate cylinders were formed adhesion layers under several conditions as shown
in Table 11A, followed further by formation of the light receiving member thereon
under the same preparation conditions as in Example lA. Separately, samples having
only adhesion layers formed thereon were prepared. The light-receiving members were
subjected to the same evaluation as in Example lA, and a part of the sample was cut
out for examination of presence or absence of crystallinity by determining the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° by means of a X-ray
diffraction device. The results are shown in Table 12.
Example 6A
[0297] On substrate cylinders were formed adhesion layers under several conditions as shown
in Table 13A, followed further by formation of the light receiving member thereon
under the same preparation conditions as in Example 1A. Separately, samples having
only adhesion layers formed thereon were prepared. The light-receiving members were
subjected to the same evaluation as in Example lA, and a part of the sample was cut
out for examination of presence or absence of crystallinity by determining the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° by means of a X-ray
diffraction device. The results are shown in Table 14A.
Example 7A
[0298] A cylinder applied with mirror surface working was further subjected to lathe working
with sword bit having various angles to prepare a plural number of cylinders having
a cross-sectional shape as shown in Fig. 35 and various cross-sectional patterns as
shown in Table 15A. Said cylinder was successively set in the prepatation device shown
in Fig. 33 and subjected to drum preparation under the preparation cinditions similarly
as in Example 1A. The drum prepared was evaluated variously by means of an electrophotographic
device of a digital exposure function with the use of a semiconductor laser having
a wavelength of 780 nm as the light source to give the results shown in Table 16A.
Example 8A
[0299] The surface of the cylinder applied with mirror surface working was applied with
the so called surface dimple formation treatment in which it was subsequently exposed
to falling of a large number of balls for bearing to form numberless hitted marks
on the cylinder surface, to prepare a plural number of cylinders having a cross-section
shape as shown in Fig. 36 and various cross-section patterns as shown in Table 17A.
Said cylinder was successively set in the preparation device shown in Fig. 33 and
subjected to drum preparation under the preparation conditions similarly as in Example
lA. The drum prepared was evaluated variously by means of an electrophotographic device
of a digital exposure function with the use of a semiconductor laser having a wavelength
of 780 nm as the light source to give the results as shown in Table 18A.
Table 1B
[0300] - - By use of the preparation device-shown in Fig_. 33, a light-receiving member
for electrophotography was formed on an aluminum cylinder applied with mirror surface
working following the preparation conditions in Table 1B. Also, by use of the device
of the same model as shown in Fig. 33, samples having only charge injection preventive
layers formed on the cylinder with the same specification were separately prepared.
The light-receiving member (hereinafter expressed as drum) was set on an electrophotographic
device, and, under various conditions, electrophotographic characteristics such as
initial charging ability, residual potential, ghost, etc., were checked, and also
lowering in charging ability, sensitivity deterioration and increase of image defects
after successive copying for 1,500,000 sheets were examined. Further, the image flow
of the drum in an atmosphere of high temperature and high humidity of 35°C and 85
% was also evaluated. And, the drum completed of evaluation was cut out at the portions
corresponding to the upper, middle and lower portions of the image portion to prepare
samples, which were provided for quantitative analysis of hydrogen contained in the
surface layer by utilization of SIMS. Also, the sample having only the charge injection
preventive layer was cut out in the same manner, and the diffraction pattern corresponding
to Si (lll) around-the diffraction angle 27° was determined by a X-ray diffraction
device for examination of presence of crystallinity. The above evaluation results,
the maximum value of the hydrogen content in the surface layer and also presence of
crystallinity of the charge injection preventive layer are comprehensively shown in
Table 2B. As shown in Table 2B, remarkable superiority was observed in the respective
items particularly of initial charging ability, image flow, residual potential, ghost,
increase of image defects and photosensitive irregularity in the axial direction,
sensitivity deterioration.
Comparative example 1B
[0301] Except for changing the preparation conditions as shown in Table 3B, the drum and
samples for analysis were prepared by the same device and method as in Example 1B
and provided for the same evaluation and analysis. The results are shown in Table
4B.
[0302] As can be seen from Table 4B, it was recognized that the respective items were inferior
as compared with Example 1B.
Example 2B
[0303] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
prepar ation conditions in Table SB.Also, by use of the device of the same model as
shown in Fig. 33, samples having only charge injection preventive layers formed on
the cylinder with the same specification were separately prepared. The light-receiving
member (hereinafter expressed as drum) was set on an electrophotographic device, and,
under various conditions, electrophotographic characteristics such as initial charging
ability, residual potential, ghost, etc., were checked, and also lowering in charging
ability, sensitivity deterioration and increase of image defects after successive
copying for 1,500,000 sheets were examined. Further, the image flow of the drum in
an atmosphere of high temperature and high humidity of 35°C and 85 % was also evaluated.
And, the drum completed of evaluation was cut out at the portions corresponding to
the upper, middle and lower portions of the image portion to prepare samples, which
were provided for quantitative analysis of hydrogen contained in the surface layer
by utilization of SIMS, and also the component profiles in the layer direction of
silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H) in the surface layer were
examined. Further, the component profiles of boron (B) and oxygen (O) in the charge
injection preventive layer were-examined. Also, the sample having only the charge
injection preventive layer was cut out in the same manner, and the diffraction pattern
corresponding to Si (111) around the diffraction angle 27° was determined by a
X-ray diffraction device for examination of presence of crystallinity. The above evaluation
results and the maximum value of the hydrogen content in the surface layer, and also
presence or absence of crystallinity of the charge injection preventive layer are
comprehensively shown in Table 6B. Further, the component profiles of said elements
in the above surface layer are shown in Fig. 37, and the component profiles of said
elements in the above charge injection preventive layer are shown in Fig. 37.
[0304] As shown in Table 6B, remarkable superiority was observed in the respective items
particularly of initial charging ability, image flow, residual potential, ghost, increase
of image defects and photosensitive irregularity in the axial direction, sensitivity
deterioration.
Example 3B, Comparative example 2B
[0305] The preparation conditions of the surface layer were changed variously as shown in
Table 7B, with other conditions being the same as in Example 1B, to prepare a plural
number of drums, which were provided for the same evaluation. And the drums completed
of evaluation were-cut out in the same manner as in Example lB to give samples, which
were subjected to the same analysis. The above results are shown in Table 8B.
Example 4B
[0306] The preparation conditions of the photoconductive layer were changed variously as
shown in Table 9B, with other conditions being the same as in Example lB, to prepare
a plural number of drums. These drums were evaluated similarly as in Example 1B to
obtain the results as shown in Table 10B.
Example 5B
[0307] The preparation conditions of the charge injection preventive layer were changed
variously as shown in Table 11B, with other conditions being the same as in Example
1B, to prepare a plural number of drums and samples having only charge injection preventive
layers formed. These drums and samples for analysis were subjected to the same evaluation
and analysis similarly as in Example 1B to obtain the results as shown in Table 12B.
Example 6B
[0308] The preparation conditions of the charge injection preventive layer were changed
variously as shown in Table 13B, with other conditions being the same as in Example
1B, to prepare a plural number of drums and samples having only charge injection preventive
layers formed. These drums and samples for analysis were subjected to the same evaluation
and analysis similarly as in Example l
B to obtain the results as shown in Table 14B.
Example 7
[0309] On a substrate cylinder, an adhesion layer was formed under several preparation conditions
as indicated in Table 15B, and further a light-receiving member was formed under-the
same preparation conditions as in Example 1B. Separately, samples having only adhesion
layers formed were prepared. The light-receiving member was subjected to the same
evaluation as in Example 1B, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 16B.
Example 8B
[0310] On a substrate cylinder, an adhesion layer was formed under several preparation conditions
as indicated in Table 17B, and further a light-receiving member was formed under the
-same preparation conditions as in Example 1B. Separately, samples having only adhesion
layers formed were prepared. The light-receiving member was subjected to the same
evaluation as in Example 1B, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 18B.
Example 9B
[0311] A cylinder applied with mirror surface working was further subjected to lathe working
with sword bit having various angles to prepare a plural number of cylinders having
a cross-sectional shape as shown in Fig. 35 and various cross-sectional patterns as
shown in Table 19B. Said cylinder was successively set in the preparation device shown
in Fig. 33 and subjected to drum preparation under the preparation conditions similarly
as in Example 1B. The drum prepared was evaluated variously by means of an electrophotographic
device of a digital exposure function with the use of a semiconductor laser having
a wavelength of 780 nm as the light source to give the results shown in Table 20B.
Example 10B
[0312] The surface of the cylinder applied with mirror surface working was applied with
the so called surface dimple formation treatment in which it was subsequently exposed
to falling of a large number of balls for bearing to form numberless hitted marks
on the cylinder surface, to prepare a plural number of cylinders having a cross-section
shape as shown in Fig. 36 and various cross-section patterns as shown in Table 21B.
Said cylinder was successively set in the preparation device shown in Fig. 33 and
subjected to drum preparation under the preparation conditions similarly as in Example
1B. The drum prepared was evaluated variously by means of an electrophotographic device
of a digital exposure function with the use of a semiconductor laser having a wavelength
of 780 nm as the light source to give the results as shown in Table 22B.
Example 1C
[0313] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the-preparation
conditions in Table 1C.The light-receiving member (hereinafter expressed as drum)
was set on an electrophotographic device, and, under various conditions, electrophotographic
characteristics such as initial charging ability, residual potential, ghost, etc.,
were checked, and also lowering in charging ability, sensitivity deterioration and
= increase of image defects after successive copying for 1,500,000 sheets were examined.
Further, the image flow of the drum in an atmosphere of high temperature and high
humidity of 35°C and 85 % was also evaluated. And, the drum completed of evaluation
was cut out at the portions corresponding to the upper, middle and lower portions
of the image portion to prepare samples, which were provided for quantitative analysis
of hydrogen contained in the surface layer by utilization of SIMS. The above evaluation
results and the maximum value of the hydrogen content in the surface layer are shown
in Table 2C. As shown in Table 2C, remarkable superiority was observed in the respective
items particularly of initial charging ability, image flow, residual potential, ghost
and photosensitive irregularity in the axial direction, sensitivity deterioration.
Comparative example 1C
[0314] Except for changing the preparation conditions as shown in Table 3C, the drum and
samples for analysis were prepared by the same device and method as in Example 1 and
provided for the same evaluation and analysis. The results are shown in Table 4C.
[0315] As can be seen from Table 4C, it was recognized that the respective items were inferior
as compared with Example 1C.
Example 2
[0316] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table 5C. The light-receiving member (hereinafter expressed
as drum) was set on an electrophotographic device, and, under various conditions,
electrophotographic characteristics such as initial charging ability, residual potential,
ghost, etc., were checked, and also lowering in charging ability, sensitivity deterioration
and increase of image defects after successive copying for 1,500,000 sheets in a real
machine were examined. Further, the image flow of the drum in an atmosphere of high
temperature and high humidity of 35°C and 85 % was also evaluated.
[0317] And, the drum completed of evaluation was cut out at the portions corresponding to
the upper, middle and lower portions of the image portion to prepare samples, which
were provided for quantitative analysis of hydrogen contained in the surface layer
by utilization of SIMS, and also the component profiles in - the layer direction of
silicon atoms (Si),carbon atoms (C) and hydrogen atoms (H) in the surface layer were
examined. Further, the component profiles of boron (
B) and oxygen (O) in the charge injection preventive layer were examined. The above
evaluation results and the maximum value of the hydrogen content in the surface layer
are shown in Table 6C. Also, the component profiles of said elements in the above
surface layer are shown in Fig. 37, and further the component profiles of said elements
in the above charge injection preventive layer are shown in Fig. 42. As shown in Table
6C, remarkable superiority was observed in the respective items particularly of initial
charging ability, image flow, residual potential, ghost and photosensitive irregularity
in the axial direction, sensitivity deterioration.
Example 3C, Comparative example 2C
[0318] The preparation conditions of the surface layer were changed variously as shown in
Table 7C, with other conditions being the same as in Example lC, to prepare a plural
number of drums and samples for analysis. These drums and samples were evaluated and
analyzed similarly as in Example lC to obtain the results as shown in Table 8C.
Example 4C
[0319] The preparation conditions of the photoconductive layer were changed variously as
shown in Table 9C, with other conditions being the same as in Example lC, to prepare
a plural number of drums. These drums were evaluated similarly as in Example 1C to
obtain the results as shown in Table 10C.
Example 5C
[0320] The preparation conditions of the charge injection preventive layer were changed
variously as shown in Table 11C, with other conditions being the same as in Example
1C, to prepare a plural number of drums. These drums were evaluated similarly as in
Example 1C to obtain the results as shown in Table 12C.
Example 6
[0321] The preparation conditions of the charge injection preventive layer were changed
variously as shown in Table 13C, with other conditions being the same as in Example
lC, to prepare a plural number of drums. These drums were evaluated similarly as in
Example 1C to obtain the results as shown in Table 14C.
Example 7C
[0322] A cylinder applied with mirror surface working was further subjected to lathe working
with sword bit having various angles to prepare a plural number of cylinders having
a cross-sectional shape as shown in Fig. 35 and various cross-sectional' patterns
as shown in Table 15C. Said cylinder was successively set in the preparation device
shown in Fig. 33 and subjected to drum preparation under the preparation conditions
similarly as in Example 1C. The drum prepared was evaluated variously by means of
an electrophotographic device of a digital exposure function with the use of a semiconductor
laser having a wavelength of 780 nm as the light source to give the results shown
in Table 16C.
Example 8
[0323] The surface of the cylinder applied with mirror surface working was applied with
the so called surface dimple formation treatment in which it was subsequently exposed
to falling of a large number of balls for bearing to form numberless hitted marks
on the cylinder surface, to prepare a plural number of cylinders having a cross-section
shape as shown in Fig. 36 and various cross-section patterns as shown in Table 17C.
Said cylinder was successively set in the preparation device shown in Fig. 33 and
subjected to drum preparation under the preparation conditions similarly as in Example
lC. The drum prepared was evaluated variously by means of an electrophotographic device
of a digital exposure function with the use of a semiconductor laser having a wavelength
of 780 nm as the light source to give the results as shown in Table 18C.
Example 1D
[0324] By use of the preparation device shown in Fig. 24, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table 1D. The light-receiving member (hereinafter expressed
as drum) was set on an electrophotographic device of a digital exposure function with
a semiconductor laser having a wavelength of 780 nm as the light source, and, under
various conditions, electrophotographic characteristics such as initial charging ability,
residual potential, ghost, etc., were checked, and also lowering in charging ability,
sensitivity deterioration and increase of image defects after successive copying for
1,500,000 sheets in a real machine were examined. Further, the image flow of the drum
in an atmosphere of high temperature and high humidity of 35°C and 85 % was also evaluated.
-And, the drum completed of evaluation was cut out at the portions corresponding to
the upper, middle and lower portions of the image portion to prepare samples, which
were provided for quantitative analysis of hydrogen contained in the surface layer
by utilization of SIMS. The above evaluation results and the maximum value of the
hydrogen content in the Fsurface layer are shown in Table 2D. As shown in Table 2D,
remarkable superiority was observed in the respective items particularly of initial
charging ability, image flow, residual potential, ghost and photosensitive irregularity
in the axial direction, sensitivity deterioration.
Comparative example 1D
[0325] Except for changing the preparation conditions as shown in Table 3D, the drum and
samples for analysis were prepared by the same device and method as in Example 1D
and provided for the same evaluation and analysis. The results are shown in Table
4D.
[0326] As can be seen from Table 4D, it was recognized that the respective items were inferior
as compared with Example lD.
Example 2D
[0327] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed-on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table 5D. The light-receiving member (hereinafter expressed
as drum) was set on an electrophotographic device of a digital exposure function with
a semiconductor laser having a wavelength of 780 nm as the light source, and, under
various conditions, electrophotographic characteristics such as initial charging ability,
residual potential, ghost, etc., were checked, and also lowering in charging ability,
sensitivity deterioration and increase of image defects after successive copying for
1,500,000 sheets in a real machine were examined. Further, the image flow of the drum
in an atmosphere of high temperature and-high humidity of 35°C and 85 % was also evaluated.
And, the drum completed of evaluation was cut out at the portions corresponding to
the upper, middle and lower portions of the image portion to prepare samples, which
were provided for quantitative analysis of hydrogen contained in the surface layer
by utilization of SIMS, and also the component profiles in the layer direction of
silicon atoms (Si), carbon atoms (C) and hydrogen atoms (H) in the surface layer were
examined. Further, the component profiles of boron (B) and oxygen (O) in the charge
injection preventive layer and the component of germanium (Ge) in the layer thickness-direction
in the longer wavelength - absorbing layer were examined. The above evaluation results
and the maximum value of the hydrogen content in the surface layer are shown in Table
6D. Also, the component profiles of said elements in the above surface layer are shown
in Fig. 37, and further the component profiles of said elements in the above charge
injection preventive layer and the component profile of said element in the longer
wavelength absorbing layer are shown in Fig. 39. As shown in Table 6D, remarkable
superiority was observed in the respective items particularly of initial charging
ability, image flow, residual potential, ghost and photosensitive irregularity in
the axial direction, sensitivity deterioration and increase of image defects as well
as interference fringe.
Example 3D, Comparative example 2D
[0328] The preparation conditions of the surface layer were changed variously as shown in
Table 7D, with other conditions being the same as in Example lD, to prepare a plural
number of drums and samples for analysis. These drums and samples were evaluated and
analyzed similarly as in Example 1D to obtain the results as shown in Table 8D.
Example 4D
[0329] The preparation conditions of the photoconductive layer were changed variously as
shown in Table 9D, with other conditions being the same as in Example ID, to prepare
a plural number of drums. These drums were evaluated similarly as in Example 1D to
obtain the results as shown in Table 10D.
Example 5
[0330] The preparation conditions of the charge injection preventive layer were changed
variously as shown in Table 11D, with other conditions being the same as in Example
1D, to prepare a plural number of drums. These drums were evaluated similarly as in
Example 1D to obtain the results as shown in Table 12D.
Example 6D
[0331] The preparation conditions of the charge injection preventive layer were changed
variously as shown in Table 13D, with other conditions being the same as in Example
1D, to prepare a plural number of drums. These drums were evaluated similarly as in
Example 1D to obtain the results as shown in Table 14D.
Example 7
[0332] The preparation conditions of the longer wavelength absorbing layer were changed
variously as shown in Table 15D, with other conditions being the same as in Example
1D, to prepare a plural number of drums. These drums were evaluated similarly as in
Example 1D to obtain the results as shown in Table 16D.
Example 8
[0333] The preparation conditions of the longer wavelength absorbing layer were changed
variously as shown in Table 17D, with other conditions being the same as in Example
1D, to prepare a plural number of drums. These drums were evaluated similarly as in
Example 1D to obtain the results as shown in Table 18D.
Example 9D
[0334] A cylinder applied with mirror surface working was further subjected to lathe working
with sword bit having various angles to prepare a plural number of cylinders having
a cross-sectional shape as shown in Fig. 29D and various cross-sectional patterns
as shown in Table 19D. Said cylinder was successively set in the preparation device
shown in Fig. 33 and subjected to drum preparation under the preparation conditions
similarly as in Example 1D. The drum prepared was evaluated variously by means of
an electrophotographic device of a digital exposure function with the use of a semiconductor
laser having a wavelength of 780 nm as the light source to give the results shown
in Table 20D.
Example 10
[0335] The surface of the cylinder applied with mirror surface working was applied with
the so called surface dimple formation treatment in which it was subsequently exposed
to falling of a large number of balls for bearing to form numberless hitted marks
on the cylinder surface, to prepare a plural number of cylinders having a cross-section
shape as shown in Fig. 36 and various cross-section patterns as shown in Table 21D.
Said cylinder was successively set in the preparation device shown in Fig. 33 and
subjected to drum preparation under the preparation conditions similarly as in Example
1D. The drum prepared was evaluated variously by means of an electrophotographic device
of a digital exposure function with the use of a semiconductor laser having a wavelength
of 780 nm as the light source to give the results as shown in Table 22D.
Example lE
[0336] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table lE. Also, by use of a device of the same model as
shown in Fig. 33, samples for analysis having only the charge injection preventive
layer and only the longer wavelength absorbing layer on the cylinder with the same
specification, respectively, were prepared separately. The light-receiving member
(hereinafter expressed as drum) was set on an electrophotographic device of a digital
exposure function with a semiconductor laser having a wavelength of 780 nm as the
light source, and, under various conditions, electrophotographic characteristics such
as initial charging ability, residual potential, ghost, etc., were checked, and also
lowering in charging ability, sensitivity deterioration and increase of image defects
after successive copying for 1,500,000 sheets in a real machine were examined. Further,
the image flow of the drum in an atmosphere of high temperature and high humidity
of 35°C and 85 % was also evaluated. And, the drum completed of evaluation was cut
out at the portions corresponding to the upper, middle and lower portions of the image
portion to prepare samples, which were provided for quantitative analysis of hydrogen
contained in the surface layer by utilization of SIMS. On the other hand, the sample
having only the charge injection preventive layer and the sample having only the longer
wavelength absorbing layer were cut out in the same manner, and then diffraction patterns
corresponding to Si (111) around the diffraction angle 27° were determined by use
of a X-ray diffraction device for examination of presence or absence of crystallinity.
The above evaluation results and the maximum valued of the hydrogen content in the
surface layer, and further presence or absence of crystallinity of the charge injection
preventive layer and the longer wavelength absorbing layer are comprehensively shown
in Table 2E. As shown in Table 2E, remarkable superiority was observed in the respective
items particularly of initial charging ability, image flow, residual potential, ghost,
image defects and photosensitive irregularity in the axial direction, sensitivity
deterioration.
Comparative example 1
[0337] Except for changing the preparation conditions as shown-in Table 3E, the drum and
samples for analysis were prepared by the same device and method as in Example lE
and provided for the same evaluation and analysis. The results are shown in Table
4E.
[0338] As can be seen from Table 4E, it was recognized that the respective items were inferior
. as compared with Example 1E.
Example 2E
[0339] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table 5E. Also, by use of a device of the same model as
shown in Fig. 33, samples for analysis having only the charge injection preventive
layer and only the longer wavelength absorbing layer on the cylinder with the same
specification, respectively, were prepared separately. The light-receiving member
(hereinafter expressed as drum) was set on an electrophotographic device of a digital
exposure function with a semiconductor laser having a wavelength of 780 nm as the
light source, and, under various conditions, electrophotographic characteristics such
as initial charging ability, residual potential, ghost, etc., were checked, and also
lowering in charging ability, sensitivity deterioration and increase of image defects
after successive copying for 1,500,000 sheets in a real machine were examined. Further,
the image flow of the drum in an atmosphere of high temperature and high humidity
of 35°C and 85 % was also evaluated. And, the drum completed of evaluation was cut
out at the portion corresponding to the upper, middle-and lower portions of the image
portion to prepare samples, which were provided for quantitative analysis of hydrogen
contained in the surface layer by utilization of SI
MS, and also the component profiles in the layer direction of silicon atoms (Si); carbon
atoms (C) and hydrogen atoms (H) in the surface layer were examined. Further, the
component profiles of boron (B) and oxygen (O) in the charge injection preventive
layer and the component of germanium (Ge) in the layer thickness direction in the
longer wavelength absorbing layer were examined. On the other hand, the sample having
only the charge injection preventive layer and the sample having only the longer wavelength
photosensitive layer were cut out in the same manner, and then diffraction patterns
corresponding to Si (lll) around the diffraction angle 27° were determined by use
of a X-ray diffraction device for examination of presence or absence of crystallinity.
The above evaluation results and the maximum value of the hydrogen content in the
surface layer, and further presence or absence of crystallinity of the charge injection
preventive layer and the longer wavelength absorbing layer are comprehensively shown
in Table 6E. Further, the component profiles of said elements in the above surface
layer are shown in Fig. 37 and the component profiles of said element in the above
charge injection preventive layer and the component profile of said element in the
longer wavelength photosensitive layer are shown in Fig. 40.
[0340] As shown in Table 6E, remarkable superiority was observed in various and many items
particularly of initial charging ability, image flow, residual potential, ghost, image
defects and photosensitive irregularity in the axial direction, sensitivity deterioration
and increase of image defects as well as interference fringe.
Example 3E, Comparative example 2E
[0341] The preparation conditions of the surface layer were changed variously as shown in
Table 7E, with other conditions being the same as in Example lE, to prepare a plural
number of drums, which were provided for the same evaluation. And, the drums completed
of evaluation were cut out into samples and subjected to the same analysis. The above
results are shown in Table 8E.
Example 4E
[0342] The preparation conditions of the photoconductive layer were changed to several conditions
as shown in Table 9E, with other conditions being the same as in Example 1E,-to prepare
a plural number of drums. These drums were evaluated similarly as in Example lE to
obtain the results as shown in Table 10E.
Example 5E
[0343] The preparation conditions of the charge injection preventive layer were changed
to several conditions as shown in Table 11E, with other conditions being the same
as in Example lE, to prepare a plural number of drums and samples having only the
charge injection preventive layer formed. These drums and samples for analysis were
subjected to evaluation and analysis as in Example 1E to obtain the results as shown
in Table 12E.
Example 6E
[0344] The preparation conditions of the charge injection preventive layer were changed
to several conditions as shown in Table 13E, with other conditions being the same
as in Example 1E, to prepare a plural number of drums and samples having only the
charge injection preventive layer formed. These drums and samples for analysis were
subjected to evaluation and analysis as in Example lE to obtain the results as shown
in Table 14E.
Example 7E
[0345] - - The preparation conditions of the longer wavelength absorbing layer were changed
to several conditions as shown in Table 15E, with other conditions being the same
as in Example lE, to prepare a plural number of drums and samples for analysis having
only longer wavelength photosensitive layer formed. The drum was subjected to the
same evaluation as in Example lE, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 16E.
Example 8
[0346] The preparation conditions of the longer wavelength absorbing layer were changed
to several conditions as shown in Table 17E, with other conditions being the same
as in Example lE, to prepare a plural number of drums and samples for analysis having
only longer wavelength absorbing layer formed. The drum was subjected to the same
evaluation as in Example lE, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 18E.
Example 9E
[0347] The preparation conditions of the longer wavelength absorbing layer were changed
to several conditions as shown in Table 19E, with other con- : ditions being the same
as in Example lE, to prepare a plural number of drums and samples for analysis having
only longer wavelength absorbing layer formed. The drum was subjected to the same
evaluation as in Example 1, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 20E.
Example 10
[0348] The preparation conditions of the longer wavelength absorbing layer were changed
to several conditions as shown in Table 21E, with other conditions being the same
as in Example 1E, to prepare a plural number of drums and samples for analysis having
only longer wavelength absorbing layer formed. The drum was subjected to the same
evaluation as in Example lE, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 22E.
Example 11
[0349] On a substrate cylinder, an adhesion layer was formed under several preparation conditions
as indicated in Table 23E, and further a light-receiving member was formed under the
same preparation conditions as in Example iE. Separately, samples having only adhesion
layers formed were prepared. The light-receiving member was subjected to the same
evaluation as in Example lE, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 24E.
Example 12E
[0350] On a substrate cylinder, an adhesion layer was formed under several preparation conditions
as indicated in Table 25E, and further a light-receiving member was formed under the
same preparation conditions as in Example E. Separately, samples having only adhesion
layers formed were prepared. The light-receiving member was subjected to the same
evaluation as in Example lE, while a part of the sample was cut out and the diffraction
pattern corresponding to Si (111) around the diffraction angle 27° was determined
for examination of presence or absence of crystallinity. The above results are shown
in Table 26E.
Example 13E
[0351] A cylinder applied with mirror surface working was further subjected to lathe working
with sword bit having various angles to prepare a plural number of cylinders having
a cross-sectional shape as shown in Fig. 35 and various cross-sectional patterns as
shown in Table 27E. Said cylinder was successively set in the preparation device shown
in Fig. 33 and subjected to drum preparation under the preparation conditions similarly
as in Example lE. The drum prepared was evaluated variously by means of an electrophotographic
device of a digital exposure function with the use of a semiconductor laser having
a wavelength of 780 nm as the light source to give the results shown in Table 28E.
Example 14
[0352] The surface of the cylinder applied with mirror surface working was applied with
the so called surface dimple formation treatment in which it was subsequently exposed
to falling of a large number of balls for bearing to form numberless hitted marks
on the cylinder surface, to prepare a plural number of cylinders having a cross-section
shape as shown in Fig. 36 and various cross-section patterns as shown in Table 29E.
Said cylinder was successively set in the preparation device shown in Fig. 33-and
subjected to drum preparation under the preparation conditions similarly as in Example
lE. The drum prepared was evaluated variously by means of an electrophotographic device
of a digital exposure function with the use of a semiconductor laser having a wavelength
of 780 nm as the light source to give the results as shown in Table 30E.
Example IF
[0353] By use of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table lF. The light-receiving member (hereinafter expressed
as drum) was set on an electrophotographic device, and, under various conditions,
electrophotographic characteristics such as initial charging ability, residual potential,
ghost, etc., were checked, and also lowering in charging ability, sensitivity deterioration
and increase of image defects after successive copying for 1,500,000 sheets in as
real machine were examined. Further, the image flow of the drum in an atmosphere of
high temperature-and high humidity of 35°C and - 85 % was also evaluated. And, the
drum completed of evaluation was cut out at the portions corresponding to the upper,
middle and lower portions of the image portion to prepare samples, which were provided
for quantitative analysis of hydrogen contained in the surface layer by utilization
of SIMS. The above evaluation results, the maximum value of the hydrogen content in
the surface layer are shown in Table 2F. As shown in Table 2F, remarkable superiority
was observed in the respective items particularly of initial charging ability, image
flow, residual potential, ghost, image defects and photosensitive irregularity in
the axial direction, sensitivity deterioration.
Comparative example 1F
[0354] Except for changing the preparation conditions as shown in Table 3F, the drum and
samples for analysis were prepared by the same device and method as in Example IF
and provided for the same evaluation and analysis. The results are shown in Table
4.
[0355] As can be seen from Table 4F, it was recognized that the respective items were inferior
as compared with Example 1F.
Example 2F
[0356] By use-of the preparation device shown in Fig. 33, a light-receiving member for electrophotography
was formed on an aluminum cylinder applied with mirror surface working following the
preparation conditions in Table 5F. The light-receiving member (hereinafter expressed
as drum) was set on an electrophotographic device, and, under various conditions,
electrophotographic characteristics such as initial charging ability, residual potential,
ghost, etc., were checked, and also lowering in charging ability, sensitivity deterioration
and increase of image defects after successive copying for 1,500,000 sheets in a real
machine were examined. Further, the image flow of the drum in an atmosphere of high
temperature and high humidity of 35°C and 85 % was also evaluated. And, the drum completed
of evaluation was cut out at the portions corresponding to the upper, middle and lower
portions of the image portion to prepare samples, which were provided for quantitative
analysis of hydrogen contained in the surface layer by utilization of SIMS, and also
the component profiles in the layer direction of silicon atoms (Si), carbon atoms
(C) and hydrogen atoms (H) in the surface layer were examined. Further, the component
profiles of boron (B) and oxygen (O) in the charge injection preventive layer and
the component profile of germanium (Ge) in the layer thickness direction in the longer
wavelength absorbing layer were examined. The above evaluation results and the maximum
value of the hydrogen content in the surface layer are shown in Table 6
F, the component profiles of said elements in the above surface layer in Fig. 37, and
the component profile of said elements in the charge injection preventive layer and
the component profile of said element in the longer wavelength photosensitive layer
in Fig. 41. As shown in Table 6F, remarkable superiority was observed in the respective
items particularly of initial charging ability, image flow, residual potential, ghost,
increase of image defects and photosensitive irregularity in the generator direction,
sensitivity deterioration and increase of image defects, as well as interference fringe.
Example 3F, Comparative example 2F
[0357] The preparation conditions of the surface layer were changed variously as shown in
Table 7F, with other conditions being the same as in Example 1F, to prepare a plural
number of drums and samples for analysis. These drums and samples were subjected to
the same evaluation and analysis as in Example 1F to obtain the results as shown in
Table 8F.
Example 4
[0358] The preparation conditions of the photoconductive layer were changed to several conditions
as shown in Table 9F, with other conditions being the same as in Example IF, to prepare
a plural number of drums. These drums were evaluated similarly as in Example 1F to
obtain the results as shown in Table 10F.
Example 5F
[0359] The preparation conditions of the charge injection preventive layer were changed
to several conditions as shown in Table 11F, with other conditions being the same
as in Example 1F, to prepare a plural number of drums. These drums were subjected
to the same evaluation similarly as in Example 1F to obtain the results as shown in
Table 12F.
Example 6F
[0360] The preparation conditions of the charge injection preventive layer were changed
to several conditions as shown in Table 13F, with other conditions being the same
as in Example 1F, to prepare a plural number of drums. These drums were subjected
to the same evaluation similarly as in Example 1F to obtain the results as shown in
Table 14F.
Example 7F
[0361] The preparation conditions of the longer wavelength absorbing layer were changed
to several conditions as shown in Table 15F, with other conditions being the same
as in Example 1F, to prepare a plural-number of drums. These drums were subjected
to the same evaluation similarly as in Example 1F to obtain the results as shown in
Table 16F.
Example 8F
[0362] The preparation conditions of the longer wavelength photosensitive layer were changed
to several conditions as shown in Table 17F, with other conditions being the same
as in Example 1F, to prepare a plural number of drums. These drums were subjected
to the same evaluation similarly as in Example 1F to obtain the results as shown in
Table 18F.
Example 9F
[0363] On a substrate cylinder, an adhesion layer was formed under several preparation conditions
as indicated in Table 19F, and further a light-receiving member was formed under the
same preparation conditions as in Example 1F. These light-receiving members were subjected
to the same evaluation as in Example 1F to obtain the results as shown in Table 20F.
-Example 10F
[0364] A cylinder applied with mirror surface working was further subjected to lathe working
with sword bit having various angles to prepare a plural number of cylinders having
a cross-sectional shape as shown in Fig. 35 and various cross-sectional patterns as
shown in Table 21F. Said cylinder was successively set in the preparation device shown
in Fig. 33 and subjected to drum preparation under the preparation conditions similarly
as in Example 1F. The drum prepared was evaluated variously by means of an electrophotographic
device of a digital exposure function with the use of a semiconductor laser having
a wavelength of 780 nm as the light source to give the results shown in Table 22F.
Example 11F
[0365] The surface of the cylinder applied with mirror surface working was applied with
the so called surface dimple formation treatment in which it was subsequently exposed
to falling of a large number of balls for bearing to form numberless hitted marks
on the cylinder surface, to prepare a plural number of cylinders having a cross-section
shape as shown in Fig. 36 and various cross-section patterns as shown in Table 23F.
Said cylinder was successively set in the preparation device shown in Fig. 33 and
subjected to drum preparation under the prepa- ration conditions similarly as in Example
1F. The drum prepared was evaluated variously by means of an electrophotographic device
of a digital exposure function with the use of a semiconductor laser having a wavelength
of 780 nm as the lightisource to give the results as shown in Table 24F.